Dissertations / Theses on the topic 'Ferroelastic'

A comprehensive study of domain switching process in different ferroelastic and ferroelastic/ferroelectric perovskite structured ceramics has been performed. The effects of thermal fluctuations on domain switching dynamics were investigated in the ferroelastic and in the ferroelectric case under static and dynamic electric and mechanical conditions. In the ferroelastic case, domain switching behaviour was investigated for different compositions, using different types of mechanical tests. Compression tests were carried out to characterize the ferroelastic properties, such as coercive stress, hysteresis loop and irreversible strain. Creep experiments were performed to study the domain switching time dependence at different stress levels. Domain switching kinetics during creep was characterized by implementing a rate model, based on thermal activation rate theory, which allowed the activation volume to be estimated. A Rayleigh-type analysis was performed to study the effects of stress amplitude, loading rate, temperature and composition on ferroelastic switching. Rayleigh-type relationships were proposed to fit the results and the rate model developed was applied to quantify the effect of the loading rate on the Rayleigh loops. Alternative methodologies were developed to assess the effects of rate and temperature on the coercive stress, providing original sets of data. A further application of the rate model provided an estimation of the activation parameters (volume and enthalpy). In PZT 5A at the coercive field the activation volume was calculated to be 2.44 nm3, with a reasonable consistency with the value obtained from creep tests (7.49 nm3). In the ferroelectric case, domain switching was studied by generating P-E and butterfly hysteresis loops and by analysing creep-relaxation curves. In creep experiments, the polarization and the strain were measured simultaneously, during the application of a constant electric field. An insight into the evolution of domain structure and on domain switching mechanisms was gained, highlighting analogies and differences with the ferroelastic case. Experiments at different frequencies, allowed the activation volume to be estimated at the coercive field (77 nm3). The relatively large value indicates small rate dependence and suggests a domain structure with broad and mobile domain walls, being the preferred sites for the nucleation.

In this thesis, ferroelastic domain switching behaviour of lead zirconate titanate ceramics, as used in devices such as actuators, was studied. In particular, the effect of cyclic frequency and amplitude were assessed to develop a correlation between macrostructural changes and fatigue behaviour, both in the bulk and in crack-tip process zones. A variety of experimental methods were used. Raman scattering enabled the poling state of the ceramics can be determined. However, it could not distinguish between the different preferred orientations of in-plane c-domains. Conversely, neutron and X-ray diffraction technique can detect domain orientation distribution and the preferred direction of c-domains. In this study, neutron diffraction was used to probe domain switching behaviour in bulk samples while high spatial resolution X-rays were employed to analyse a switching zone near a crack tip. Under cyclic mechanical loading, domain switching and the accumulation of ferroelastic strain becomes saturated with increasing number of cycles. Moreover, time-dependent deformation was investigated. The results show that a domain forward-switching process occurs during creep deformation while a domain backward-switching process takes place during recovery. In addition, it was found that the frequency of applied stress affects the saturation of the ferroelastic strain while its magnitude has an influence on the level of strain accumulated. Under static mechanical loading, it was found that the size of the crack-tip zone where stress-induced domain switching occurs with increase in the stress intensity factor but the degree of domain switching around the crack tip changes only slightly. Under cyclic electrical loading, the results present a strong link between the frequency of the applied field, remnant polarisation, domain switching and the resultant crack growth. The results show that polarisation fatigue, the size of the switching zone, and the crack growth rate is greater at lower loading frequency. The quantitative analysis of the time dependent mechanism as well as the effect of loading frequency and amplitude on domain switching was achieved by applying viscoelastic models. Importantly, these models can be used to explain domain switching behaviour and domain wall movement under cyclic loading and link these processes to macroscopic deformation.

Ferroelectric-reinforced metal matrix composites (FR-MMCs) offer the potential to improve damping characteristics of structural materials. Many structural materials are valued based on their stiffness and strength; however, stiff materials typically have limited inherent ability to dampen mechanical or acoustic vibrations. The addition of ferroelectric ceramic particles may also augment the strength of the matrix, creating a multifunctional composite. The damping behavior of two FR-MMC systems has been examined. One involved the incorporation of barium titanate (BaTiO3) particles into a Cu- 10w%Sn (bearing bronze) matrix and the other incorporating them into an electroformed Ni matrix. Here the damping properties of the resulting ferroelectric reinforced metal matrix composites (FR-MMCs) have been investigated versus frequency, temperature (above and below the Curie temperature of the reinforcement), and number of strain cycles. FR-MMCs currently represent a material system capable of exhibiting increased damping ability, as compared to the structural metal matrix alone. Dynamic mechanical analysis and neutron diffraction have shown that much of this added damping ability can be attributed to the ferroelectric/ferroelastic nature of the reinforcement.
Ph. D.

Ferroelectric and piezoelectric ceramic reinforced metal matrix composites are new materials being explored for vibration damping purposes. The high damping ability of ferroelectric and piezoelectric ceramics such as barium titanate (BaTiO3) and lead zirconate titanate (PZT) is due to the anelastic response of ferroelastic domain walls to applied external stress. In piezoelectric ceramics, vibration energy can also be dissipated through the direct piezoelectric effect if the appropriate electric circuit is connected across the ceramic. In this work we have examined the vibration damping behavior of BaTiO3, nickel-barium titanate (Ni-BaTiO3) composites and nickel-lead zirconate titanate (Ni-PZT) composites. BaTiO3 ceramics were fabricated by a combination of uniaxial pressing and cold isostatic pressing followed by sintering in air. Low frequency (0.1Hz-10Hz) damping capacity of BaTiO3, tanδ has been measured in three-point bend configuration on a dynamic mechanical analyzer. Tanδ has been found to increase with temperature up to the Curie temperature (Tc) of BaTiO3, after which there was a drop in damping capacity values due to the disappearance of ferroelectric domains above Tc. Furthermore within the frequency range tested, tanδ has been found to decrease with increasing vibration frequency. We also observed that tanδ decays with the number of vibration cycles (N). The decrease in tanδ with N, however, is fully recovered if BaTiO3 is heated above the Tc. Ni-BaTiO3 composite composed of a layer of BaTiO3 ceramic sandwiched between two layers of Ni were fabricated using a combination of electroless plating and electroforming. The damping behavior of the composite was analyzed in terms of the damping mechanisms below Tc and the damping mechanisms above Tc of BaTiO3. Below Tc, vibration damping ability of the composite was highly influenced by ferroelastic damping in the BaTiO3 component. Above the Curie temperature, the damping capacity was influence more by the inherent damping mechanisms in the nickel matrix. The damping mechanisms in Ni-PZT composites were evaluated at a low vibration frequency of 1Hz. In these composites we identified ferroelastic domain wall motion as the main damping mechanism active below the Tc of PZT. Using a poled PZT ceramic enhanced the damping capacity of the composite because of favorable ferroelastic domain orientation in the direction of applied stress. Based on our experimental results, we found no evidence of a direct piezoelectric damping mechanism in the Ni-PZT composites.
Ph. D.

Low-dimensional materials with novel electronic and ferroic properties play a crucial role in the development of next-generation nanoscale functional devices and have drawn extensive research attentions. By using state-of-art first-principles calculations, Monte Carlo simulations, and structural revolution algorithms, four new low-dimensional materials were predicted showing promising applications in electronics or spintronics and two strategies were proposed to introduce ferroelectricity and realize strong electromagnetic coupling in experimentally fabricated low-dimensional materials, which may accelerate the discovery and design of novel functional low-dimensional materials.

ARAÚJO, Bruno Sousa. Transições de fase induzidas por pressão e tamanho de partícula no ferroelástico Pb8O5(VO4)2. 2014. 79 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2014.
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Ferroelastic compounds are characterized by the possibility to present two or more states of spontaneous strain which could be permuted by application of mechanical stress. Pb8O5(VO4)2 can be classified as belonging to this group. Its crystal structure is not well defined in the literature due to certain adversities found during the data analysis. However, making use of X-ray diffraction in several crystals of this compound we will discuss their probable point groups. It is also known that there is a direct relation between the states of strain and the domains pattern at ambient conditions of temperature and pressure. Several spectroscopic techniques were employed in order to analyze how the crystal structure of these compounds varies according to the dimensions of each crystal. Therefore, we observed the existence of three phases under ambient conditions as well as the possibility of a spontaneous phase transition in crystals of order to units of square micrometers. The structural behavior of Pb8O5(VO4)2 with increasing temperature has been studied in detail by different authors. They reported the existence of two phase transitions on heating, one second-order transition at about 440 K and another first-order around 520 K. The first-order phase transition leads the Pb8O5(VO4)2 crystals of ferroelastic phase to paraelastic phase. However, since ferroelastics crystals show changes of state of spontaneous strain through the application of mechanical stress, we made use of Raman scattering measures with increasing of hydrostatic pressure on samples of Pb8O5(VO4)2 to accompany the spectral behavior of the same during these pressure variations. This way we observed a phenomenon of amorphization of the sample around 11 GPa and obtained strong evidences from three phase transitions at approximately 1, 3.5 and 6 GPa.
Compostos ferroelásticos são caracterizados pela possibilidade de apresentarem dois ou mais estados de deformação ou strain espontâneos devendo haver a possibilidade de permutação entre estes estados através da aplicação de um stress mecânico. O Pb8O5(VO4)2 pode ser classificado como pertencente a este grupo. Sua estrutura cristalina ainda não é bem definida na literatura por conta de certas adversidades encontradas durante as análises das mesmas, no entanto, fazendo uso de difração de raios-X em diversos cristais deste composto discutiremos seus prováveis grupos pontuais. Sabe-se também que há uma relação direta entre os estados de strain e as estruturas de domínios sob condições ambientes de temperatura e pressão. Diversas técnicas espectroscópicas foram empregadas afim de analisar como a estrutura cristalina destes compostos pode variar de acordo com as dimensões de cada cristal. Dessa forma, verificamos a existência de três fases sob condições ambiente, bem como a possibilidade de uma transição de fase espontânea para cristais da ordem de unidades de micrometros quadrados. O comportamento estrutural do Pb8O5(VO4)2 com o aumento de temperatura foi estudado detalhadamente por diversos autores. Eles reportaram a existência de duas transições de fase durante o aquecimento, uma transição de segunda ordem por volta de 440 K e outra de primeira ordem por volta de 520 K. A transição de primeira ordem leva os cristais de Pb8O5(VO4)2 da fase ferroelástica para a fase paraelastica. Contudo, uma vez que cristais ferroelásticos apresentam mudanças de estados de strain espontâneos através da aplicação de stress mecânico, fizemos uso de medidas de espalhamento Raman com aumento de pressão hidrostática em amostras de Pb8O5(VO4)2 para acompanhar o comportamento espectral dos mesmos durante estas variações de pressão. Assim, observamos um fenômeno de amorfização da amostra por volta de 11 GPa e obtivemos fortes indícios de três transições de fase em aproximadamente 1, 3.5 e 6 GPa.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico
Compostos ferroelÃsticos sÃo caracterizados pela possibilidade de apresentarem dois ou mais estados de deformaÃÃo ou strain espontÃneos devendo haver a possibilidade de permutaÃÃo entre estes estados atravÃs da aplicaÃÃo de um stress mecÃnico. O Pb8O5(VO4)2 pode ser classificado como pertencente a este grupo. Sua estrutura cristalina ainda nÃo à bem definida na literatura por conta de certas adversidades encontradas durante as anÃlises das mesmas, no entanto, fazendo uso de difraÃÃo de raios-X em diversos cristais deste composto discutiremos seus provÃveis grupos pontuais. Sabe-se tambÃm que hà uma relaÃÃo direta entre os estados de strain e as estruturas de domÃnios sob condiÃÃes ambientes de temperatura e pressÃo. Diversas tÃcnicas espectroscÃpicas foram empregadas afim de analisar como a estrutura cristalina destes compostos pode variar de acordo com as dimensÃes de cada cristal. Dessa forma, verificamos a existÃncia de trÃs fases sob condiÃÃes ambiente, bem como a possibilidade de uma transiÃÃo de fase espontÃnea para cristais da ordem de unidades de micrometros quadrados. O comportamento estrutural do Pb8O5(VO4)2 com o aumento de temperatura foi estudado detalhadamente por diversos autores. Eles reportaram a existÃncia de duas transiÃÃes de fase durante o aquecimento, uma transiÃÃo de segunda ordem por volta de 440 K e outra de primeira ordem por volta de 520 K. A transiÃÃo de primeira ordem leva os cristais de Pb8O5(VO4)2 da fase ferroelÃstica para a fase paraelastica. Contudo, uma vez que cristais ferroelÃsticos apresentam mudanÃas de estados de strain espontÃneos atravÃs da aplicaÃÃo de stress mecÃnico, fizemos uso de medidas de espalhamento Raman com aumento de pressÃo hidrostÃtica em amostras de Pb8O5(VO4)2 para acompanhar o comportamento espectral dos mesmos durante estas variaÃÃes de pressÃo. Assim, observamos um fenÃmeno de amorfizaÃÃo da amostra por volta de 11 GPa e obtivemos fortes indÃcios de trÃs transiÃÃes de fase em aproximadamente 1, 3.5 e 6 GPa.
Ferroelastic compounds are characterized by the possibility to present two or more states of spontaneous strain which could be permuted by application of mechanical stress. Pb8O5(VO4)2 can be classified as belonging to this group. Its crystal structure is not well defined in the literature due to certain adversities found during the data analysis. However, making use of X-ray diffraction in several crystals of this compound we will discuss their probable point groups. It is also known that there is a direct relation between the states of strain and the domains pattern at ambient conditions of temperature and pressure. Several spectroscopic techniques were employed in order to analyze how the crystal structure of these compounds varies according to the dimensions of each crystal. Therefore, we observed the existence of three phases under ambient conditions as well as the possibility of a spontaneous phase transition in crystals of order to units of square micrometers. The structural behavior of Pb8O5(VO4)2 with increasing temperature has been studied in detail by different authors. They reported the existence of two phase transitions on heating, one second-order transition at about 440 K and another first-order around 520 K. The first-order phase transition leads the Pb8O5(VO4)2 crystals of ferroelastic phase to paraelastic phase. However, since ferroelastics crystals show changes of state of spontaneous strain through the application of mechanical stress, we made use of Raman scattering measures with increasing of hydrostatic pressure on samples of Pb8O5(VO4)2 to accompany the spectral behavior of the same during these pressure variations. This way we observed a phenomenon of amorphization of the sample around 11 GPa and obtained strong evidences from three phase transitions at approximately 1, 3.5 and 6 GPa.

The primary focus of this research is to investigate the non-linear behavior of single crystal and polycrystalline relaxor ferroelectric PMN-xPT and PZN-xPT through experimentation and modeling. Characterization of single crystal and polycrystalline specimens with similar compositions was performed. These data give experimental insight into the differences that may arise in a polycrystal due to local interaction with inhomogeneities. Single crystal specimens were characterized with a novel experimental technique that reduced clamping effects at the boundary and gave repeatable results. The measured experimental data was used in conjunction with electromechanical characterizations of other compositions of single crystal specimens with the same crystallographic orientation to study the compositional effects on material properties and phase transition behavior. Experimental characterization provided the basis for the development of a model of the continuous phase transformation behavior seen in PMN-xPT single crystals. In the modeling it is assumed that a spatial chemical and structural heterogeneity is primarily responsible for the gradual phase transformation behavior observed in relaxor ferroelectric materials. The results are used to simulate the effects of combined electrical and mechanical loading. An improved rate-independent micromechanical constitutive model based on the experimental observations of single crystal and polycrystalline specimens under large field loading is also presented. This model accounts for the non-linear evolution of variant volume fractions. The micromechanical model was calibrated using single crystal data. Simulations of the electromechanical behavior of polycrystalline ferroelectric materials are presented. These results illustrate the effects of non-linear single crystal behavior on the macroscopic constitutive behavior of polycrystals.

Durant ce travail de thèse, nous avons étudié l’effet d’un champ électrique intense (>3 kV.cm-1) sur des matériaux à structures pérovskites, le ferroélastique CaTiO3 et le ferroélectrique BaTiO3. Un tel champ agit comme une force extérieure dans la sélection, l’orientation et la distribution des domaines. Son application durant la croissance modifie la nucléation, le coefficient de partage des espèces et la possible modification du diagramme de phase du matériau considéré. En effet les ions dans un champ électrique voient leur énergie changer ce qui implique un nouvel équilibre thermodynamique. La première partie est dédiée à la croissance cristalline de CaTiO3 lorsque plusieurs paramètres de croissance sont modifiés (vitesse de croissance vG et potentiel électrique V). En faisant varier ces paramètres, nous montrons que nous pouvons contrôler la morphologie du cristal et ainsi altérer l’orientation cristalline des domaines. Des résultats similaires sont retrouvés avec BaTiO3.Plusieurs techniques expérimentales ont été employées dans le but d’étudier la microstructure des composés notamment la microscopie électronique miroir (MEM) et la microscopie électronique à faible énergie (LEEM) afin de caractériser les domaines et parois de domaines à la surface du titanate de calcium. La polarité de ces parois ayant été récemment prouvée, nous avons étudié et comparé le potentiel de surface entre les échantillons qui ont été élaborés sous et sans champ électrique
In this work, we investigate electric field effect (>3 kV.cm-1) on perovskite compound, CaTiO3 (ferroelastic) and BaTiO3 (ferroelectric). This electric field acts like an external force in selection, orientation and distribution of piezoelectric/ferroelastic domains. The electric field can act on nucleation, the partition coefficient of species and the possible modification phases diagrams of a material during its growth. Indeed ions within an electric field see their energy changing which implies a new thermodynamic equilibrium.In the first part, we discuss about crystal growth of CaTiO3 with different growth parameters (velocity of cristal growth vG, electric potential V). By varying this parameters, we can control crystal shape and can alter the crystalline orientation of domains. Same results are found with BaTiO3.In a second step, we used Mirror Electron Micrsocopy (MEM) and Low Energy Electron Microscopy (LEEM) to caracterize domains walls at the surface of calcium titanate. Polarity of domains walls have been prooved recently, and so we have investigated surface potential between samples grown under or without electric field

Ce travail de thèse porte sur les propriétés structurales et électroniques des parois de domaines ferroïques ; il a pour objectif une meilleure compréhension des mécanismes de conduction dans les parois de domaines du niobate de lithium d’une part, et de la polarité des parois de domaine dans le titanate de calcium d’autre part. La première partie est consacrée aux interactions entre les défauts et les parois de domaine dans le niobate de lithium. L’observation d’une relaxation diélectrique de faible énergie d’activation et l’analyse de son comportement sous l’effet d’un recuit dans des échantillons avec et sans parois nous conduisent à proposer que les parois de domaines stabilisent des états polaroniques. Nous rapportons aussi l'évolution de modes Raman dans des échantillons congruents de niobate de lithium dopés de manière croissante en magnésium. Nous identifions des décalages en fréquence spécifiques aux parois de domaines. Les parois de domaines apparaissent alors comme des lieux de stabilisation des défauts polaires. Nous utilisons la microscopie électronique miroir (MEM) et la microscopie électronique de faible énergie (LEEM) pour caractériser les domaines et parois de domaines à la surface du niobate de lithium dopé magnésium. Nous démontrons que les réglages de la distance focale peuvent être utilisés pour déterminer la polarisation du domaine. Aux parois de domaines, un champ électrique latéral, provenant de différents états de charge de surface, est mis en évidence. Dans une seconde partie, nous étudions la polarité des parois de domaine dans le titanate de calcium. Nous utilisons la spectroscopie de résonance piézo-électrique pour mettre en évidence l’excitation de résonances élastiques par un signal électrique, ce qui est interprété comme une réponse piézoélectrique des parois de domaines. Une image directe des parois de domaine du titanate de calcium est obtenue par LEEM, et montre une différence de potentiel de surface entre domaines et parois. Ce contraste peut être modifié sous l’effet d’injection d’électrons, par un effet d’écrantage des charges de polarisation aux parois
We investigate the structural and electronic properties of domain walls to achieve a better understanding of the conduction mechanisms in domain walls of lithium niobate and the polarity of domain walls in calcium titanate. In a first part, we discuss the interaction between defects and domain walls in lithium niobate. A dielectric resonance with a low activation energy is observed, which vanishes under thermal annealing in monodomain samples while it remains stable in periodically poled samples. Therefore we propose that domain walls stabilize polaronic states. We also report the evolution of Raman modes with increasing amount of magnesium in congruent lithium niobate. We identified specific frequency shifts of the modes at the domain walls. The domains walls appear then as spaces where polar defects are stabilized. In a second step, we use mirror electron microscopy (MEM) and low energy electron microscopy (LEEM) to characterize the domains and domain walls at the surface of magnesium-doped lithium niobate. We demonstrate that out of focus settings can be used to determine the domain polarization. At domain walls, a local stray, lateral electric field arising from different surface charge states is observed. In a second part, we investigate the polarity of domain walls in calcium titanate. We use resonant piezoelectric spectroscopy to detect elastic resonances induced by an electric field, which is interpreted as a piezoelectric response of the walls. A direct image of the domain walls in calcium titanate is also obtained by LEEM, showing a clear contrast in surface potential between domains and walls. This contrast is observed to change reversibly upon electron irradiation due to the screening of polarization charges at domain walls

Les etudes sur la deflexion de la lumiere comme outil d'investigation pour le physicien du solide d'une part et sur des cristaux ferroelastiques avec une attention concernant l'apfa d'autre part, sont presentees dans ce travail. Premierement l'analyse de la deflexion en fonction de l'angle d'incidence est effectue en detail, en ce qui concerne les angles de deflexion aussi que la polarisation des rayons deflechis. Ensuite, l'intensite des rayons a ete etudiee en comparaison avec des phenomenes de diffraction et, les parametres physiques agissant (proprietes optiques, nombre de domaines) sont abordes. L'utilisation de la deflexion pour la comprehension des ferroelastiques (les changements de symetrie lors des transitions, la birefringence) est proposee. Un cristal particulier a ete etudie (l'apfa) par analyse simultanee des resultats de deflexion et des autres mesures physiques (constantes dielectriques, proprietes optiques et observation des domaines).

Utilisés dans de nombreux domaines, les matériaux piézoélectriques sont régulièrement soumis à des sollicitations externes ou internes qui modifient leurs propriétés. Dans le but de prévoir et d'anticiper ces altérations, ce travail étudie les propriétés de matériaux piézoélectriques soumis à une contrainte statique de type mécanique ou électrique. Dans un premier temps, nous développons les équations du mouvement d'un matériau piézoélectrique (non hystérétique) au second ordre, en tenant compte à la fois des déformations dynamiques occasionnées par le passage de l'onde, mais aussi des déformations statiques concomitantes à la présence de contraintes. L'étude numérique des vitesses en onde plane et du coefficient de couplage est faite sur un matériau de référence (le niobate de lithium), dans différents plans de coupe et dans les différents systèmes de coordonnées (naturel et prédéformé). Ainsi, on évalue dans quelles configurations l'application d'une contrainte externe de type électrique ou mécanique améliore ou dégrade les propriétés du matériau. Dans une seconde partie, nous caractérisons les comportements hystérétiques de piézocéramiques sous contrainte (uniaxiale) mécanique et électrique en modélisant l'évolution des polarisations et déformations rémanentes microscopiques via les mouvements de murs de domaines. La comparaison des résultats numériques avec des évolutions issues de la littérature de 4 piézocéramiques nous permet de définir le domaine de validation de nos hypothèses et d'expliciter les comportements hystérétiques de piézocéramiques dites " dures " et " molles ". L'étude de l'évolution des constantes du matériau a permis de mettre en avant des comportements propres aux différents types de piézocéramiques ainsi que les avantages et limites de notre modèle. Dans une dernière partie, nous mettons en place un dispositif expérimental de mesure de déformations (longitudinale et transversales), ainsi que du déplacement électrique de deux piézocéramiques (une molle, le Pz21, et une dure, le Pz26) et du niobate de lithium sous contrainte mécanique (uniaxiale). Ces résultats nous ont permis de dimensionner notre étude sur le niobate de lithium et apportent une meilleure compréhension de l'évolution des déformations transversales dans les piézocéramiques.

Thermal barrier coatings (TBCs) have become an important part of turbine technology by providing thermal protection to the underlying metallic components. These coatings are typically made from a zirconia-based ceramics which have a low thermal conductivity and thermal expansion coefficients similar to those of the superalloys. Early failure in these coatings is most often due to foreign object damage and erosion resulting in delamination and spallation. To protect against these types of failure, new materials with increased toughness are needed. There are two main toughening mechanisms in ceramics: transformation toughening, which is limited to low temperature applications and ferroelastic toughening which is accessible at all temperatures. Ferroelastic toughening occurs when the c-axis of the tetragonal grain undergoes reorientation under the application of an external stress. In this study, ferroelastic toughening is examined by Raman spectroscopy. It is shown that by using polarized confocal Raman spectroscopy one can not only observed the ferroelastic process, but also measure the parameters that control the increase in toughness observed. Ferroelastic toughening was observed in two ways in the 18mol% ceria stabilized zirconia (18CSZ) samples studied here. Samples were either exposed to indentation damage or uniaxial loading. In both of these cases maps of the ceramic surface were taken using Raman spectroscopy following loading and the relative intensities of the tetragonal peaks were analyzed. The resulting intensity profiles were used to monitor the reorientation of domains corresponding to ferroelastic toughening. Changes in domain orientation were observed that corresponded to the reorientation of domains along cracks as well as on a larger scale along those cracks. Domain reorientation was also observed under uniaxial loading and the stresses required for domain formation and movement were measured.

Abstract Ferroelectric/ferroelastic ceramics are used in a range of smart structure applications, such as actuators and sensors due to their electromechanical coupling properties. However, their inherent brittleness makes them susceptible to cracking and understanding their fracture is of prominent importance. A numerical study for a stationary, plane strain crack in a ferroelastic material is performed as part of this work. The stress and strain fields are analyzed using a constitutive law that accounts for the strain saturation, asymmetry in tension versus compression, Bauschinger effects, reverse switching, and remanent strain reorientation that can occur in these materials due to the non-proportional loading that arises near a crack tip. The far-field K-loading is applied using a numerical method developed for two-dimensional cracks allowing for the true infinite boundary conditions to be enforced. The J -integral is computed on various integration paths around the tip and the results are discussed in relation to energy release rate results for growing cracks and for stationary cracks in standard elastic–plastic materials. In addition to the fracture studies, we examine the far field electromechanical loading conditions that favor the formation, existence and evolution of stable needle domain array patterns, using a phase-field modeling approach. Such needle arrays are often seen in experimental imaging of ferroelectric single crystals, where periodic arrays of needle-shaped domains of a compatible polarization variant coexist with a homogeneous single domain parent variant. The infinite arrays of needles are modeled via a representative unit cell and the appropriate electrical and mechanical periodic boundary conditions. A theoretical investigation of the generalized loading conditions is carried out to determine the sets of averaged loading states that lead to stationary needle tip locations. The resulting boundary value problems are solved using a non-linear finite element method to determine the details of the needle shape as well as the field distributions around the needle tips.
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Ferroelectric materials find application in numerous electronic devices and are continuously enabling the development of new technologies. Their versatility is intimately related to the unique property to switch the polarization with electric fields. However, the switching mechanisms in polycrystalline ferroelectric materials remain insufficiently understood. Several questions regarding the mechanisms of the polarization reversal process in polycrystalline ceramic materials have been addressed in this work. The dynamics of the process was measured by a self-constructed high voltage switch, which provides high voltage pulses to the sample and measures its macroscopic polarization and strain response over several decades. Moreover, this macroscopic technique was supplemented by in situ synchrotron diffraction experiments using a high speed detector at the European Synchrotron Radiation Facility. This unique combination of macroscopic and microscopic time-resolved experimental data allowed to reveal the sequence of events during polarization switching in polycrystalline ferroelectric materials. The process is illustrated by a sequence of well-defined 180° and non-180° domain switching events, which can be separated into three regimes. Field-dependent measurements allow to determine activation fields for the individual regimes, which are a crucial input parameter for micromechanical models. The domain structure in a poled polycrystalline ferroelectric/ferroelastic material mainly consists of non-180° domain walls. Several of them are misaligned to the poling field direction and polarization reversal can start from these misaligned domains. In the first switching regime, the non-180° domain walls are moving, driven by an external applied electric field and supported by internal mechanical fields. Auxiliary mechanical forces and the fact that nuclei are already available result in a low activation field and consequently a fast movement of the domain walls. The transition between the first and the second regime is governed by the interplay between electric and mechanical fields, which can be displayed by Landau energy landscapes. The polarization reversal in the second regime occurs by 180° or synchronized non-180° domain wall movement. Hereby, more than 60% of the total polarization was found to be switched in a model Pb(Zr,Ti)O3 material. With the experimental methods available today, it is not possible to distinguish between pure 180° or synchronized non-180° domain wall movement. However, a more than three times lower Peierls barrier for non-180° compared to 180° domain wall movement and crystallographic arguments suggest that switching in the main switching phase occurs essentially by synchronized non-180° events. In any case, the mechanical stress in this regime is acting against the moving domain walls, which is expressed by a 35% higher activation field, as compared to the first regime. In the third regime the majority of domains are reversed and the electric field is parallel to the polarization vector. Here, creep-like movement of non-180° domain walls occurs. The dynamic response of polycrystalline ceramic materials is strongly influenced by their microstructure, affecting the polarization and strain response in the individual regimes. In this context, the velocity of domain walls is set by the local electric field. The distribution of the latter in a polycrystalline ceramic material is inhomogeneous, since it represents a projection of the external electric field to the direction of the spontaneous polarization of a grain. In addition, other factors influence the dynamic response. A 47 % higher activation field was found for Pb(Zr,Ti)O3 materials with a tetragonal compared to a material with a rhombohedral crystallographic structure. This partially reflects the influence of the lattice distortion and the resulting internal stresses at the domain junctions, which have to be overcome when the domain walls are moving. In addition, mechanical and electrical interaction between grains play a significant role. In this context, internal mechanical stresses may enhance or suppress domain wall movement. This is for example expressed in a broader distribution of switching times for a polycrystalline ceramic with smaller grain sizes compared to a ceramic material with larger grain sizes. On the other hand, a 20 % reduction in the activation field for polarization reversal was found for BaTiO3-based materials which are highly crystallographically textured compared to untextured materials. Tailoring the microstructure accordingly may impede or facilitate the dynamic response of the polycrystalline ceramic material. In addition, a relation between microstructural parameters and the dynamic polarization response of polycrystalline ferroelectric ceramic materials is an important input parameter for theoretical models.

This cumulative Habilitation thesis summarizes several examples related to the application of Raman spectroscopy for the investigation of coupling phenomena induced by epitaxially, mechanically or piezoeletrically applied strain. Methods for quantitative determination of strain by Raman spectroscopy are proposed for some materials such as BiFeO3 or strained Si. Raman spectroscopy was also used for understanding temperature induced phase transitions or orbital ordering, which are intimately related to specific phonon modes, as in the case of BiCrO3 or LaVO3, respectively. A method based on the Raman tensor formalism, which allows an assignment of the BiFeO3 Raman modes of pure as well as mixed character/symmetries is proposed. Relying on this assignment it is shown that Raman spectroscopy is a powerful tool for the investigation of ferroelastic domain formation in multiferoic materials, being able to probe the tilt of the domain walls.

碩士
國立中山大學
材料與光電科學學系研究所
98
The composition dependent variation of ferroelectric domain structure in lead zirconate titanate (Pb(Zr0.52Ti0.48)O3) ceramics have been investigated within the morphotropic phase boundary (MPB). Tetragonal phase in sintered samples were identified via X-ray diffractometry (XRD). Representative microstructures of ferroelectric domains were examined using scanning electron microscopy (SEM). α-boundaries, δ- boundaries, and π-boundaries were analyzed from the contrast of extreme fringe patterns by transmission electron microscopy (TEM). Twin planes for 90o domains lie in {011) and for 180o domains lie in {100) and {220) were determined by selected area diffraction patterns (SADP). Traditional contrast analysis was adopted for determining displacement vectors (R). 90o domains with R = ε[011] and 180o domains with R = n[001]. Convergent beam electron diffraction (CBED) was performed to identify crystalline phases of different domain configurations. By examined the symmetry along the Z = [100], [110], and [111] zone axis, both δ-boundaries and π-boundaries are tetragonal phase.

The polarization response such as ferroelectric and ferroelastic switching in ferroelectrics is the important feature for ferroelectric and electromechanical applications. In polycrystalline form ferroelectrics, effects of the microstructural parameters such as texture, grain size, and residual stress are there and have not fully been understood. Among these effects, (1) the origin of grain size effects on ferroelastic switching, (2) mechanical stress effects on polarization switching, and (3) ferroelectric switching kinetics and the relationship to grain boundaries are investigated.
Firstly, the microscopic origin of ferroelastic switching suppression in smaller grains is discovered using a microscopic probing technique (piezoresponse force microscopy). It is demonstrated that there is no independent grain size effect on ferroelastic switching; the grain size affects the domain structure in a grain, and the domain structure plays an important role in the ferroelastic switching suppression. This result suggests that the grain size is not an independent critical parameter for the electromechanical property degradation in a grain < 1 m as the ferroelastic switching is a dominant component for the electromechanical property.
The study about the mechanical stress effects on the electric field induced polarization switching rationalizes the emergence of the electric field induced low-symmetry phases observed in tetragonal Pb(Zr,Ti)O3 and BaTiO3 ceramics after poling. It is demonstrated that a shear stress plays an important role in stabilizing the monoclinic phase in Pb(Zr,Ti)O3 whereas a normal stress along the polarization axis is a key for the monoclinic phase in BaTiO3 with a thermodynamic approach. It is suggested that the fraction of the low-symmetry phase, which is important for the large electromechanical property, can be engineered by applying an appropriate stress.
For the work about ferroelectric switching kinetics, the first direct Barkhausen noise associated with ferroelectric switching is measured. The domain switching time is quantified by the frequency of the Barkhausen noise. It is discovered that the dominant domain wall pinning site is grain boundaries based on the domain wall jump distance between pinning sites calculated from the switching time. This result suggests that the technique is a good tool for understanding the relationship between microstructure – domain wall kinetics.
In sum, the mechanisms of the polarization switching suppression due to domain structure and grain boundaries, and the emergence of the low symmetry phases due to stresses are revealed. These discoveries facilitate further improvements of the device performances with engineering the domain structure, grain boundaries and residual stress.

The thesis entitled “In situ crystallography and charge density analysis of phase transitions in complex inorganic sulfates” consists of six chapters. Structural changes exhibited by ferroic and conducting materials are studied as a function of temperature via in situ crystallography on the same single crystal. These unique experiments bring out the changes in the crystal system resulting in subtle changes in the complex polyhedra, distortions in bond lengths and bond angles, rotation of sulfate tetrahedral around metal atoms, phase separations and charge density features. The results provide new insights into the structural changes during the phase transition in terms of coordination changes, variable bond paths and variability in electrostatic potentials while suggesting possible reaction pathways hitherto unexplored. Chapter 1 gives a brief review of the basic features of structural phase transitions in terms of types of phase transitions, their mechanisms and related properties and outlines some of the key characterization techniques employed in structural phase transition studies like single crystal diffraction, thermal analysis, conductivity, dielectric relaxation, Raman spectroscopy and charge density studies. Chapter 2 deals with the group of compounds A3H(SO4)2, where A= Rb, NH4, K, Na which undergoes ferroelastic to paraelastic phase transitions with increase in temperature. Crystal structures of these compounds have been determined to a high degree of accuracy employing the same single crystal at room temperature at 100K and at higher temperatures. The data collection at 100K allows the examination of the ordered and disordered hydrogen atom positions. Rb3H(SO4)2 show two intermediate phases before reaching the paraelastic phase with increase in temperature. However, in case of (NH4)3H(SO4)2 and K3H(SO4)2, the paraelastic phase transition involves a single step. Chapter 3 deals with variable temperature in situ single crystal X-ray diffraction studies on fast super protonic conductors AHSO4, where A= Rb, NH4, K to characterize the structural phase transitions as well as the dehydration mechanism. The structure of KHSO4 at room temperature belongs to an orthorhombic crystal system with the space group symmetry Pbca and on heating to 463K it transforms to a C centered orthorhombic lattice, space group Cmca. The high temperature structure contain two crystallographically independent units of KHSO4 of which one KHSO4 unit is disordered at oxygen and hydrogen sites an shows a remarkable increase of sulfur oxygen bond distance – 1.753(4)Å. On heating to 475K, two units of disordered KHSO4 combine and loose one molecule of water to result in a structure K2S2O7 along with an ordered KHSO4 in a monoclinic system [space group P21/c]. On further heating to 485K two units of ordered KHSO4 combine, again to lose one water molecule to give K2S2O7 in a monoclinic crystal system [space group C2/c]. In the case of RbHSO4, both the high temperature structural phase transition and a serendipitous polymorph have been characterized by single crystal X-ray diffraction. The room temperature structure is monoclinic, P21/n, and on heating the crystal insitu On the diffractometer to 460K the structure changes to an orthorhombic system [space group Pmmn]. On keeping the crystallization temperature at 80°C polymorph crystals of RbHSO4 were grown. In case of NH4HSO4 both the room temperature and high temperature structures are structurally similar to those in RbHSO4, but the transition temperature is found to be 413K. Chapter 4 deals with the crystal structure, ionic conduction, dielectric relaxation, Raman spectroscopy phase transition pf a fast ion conductor Na2Cd(SO4)2. The structure is monoclinic, space group C2/c, and is built up with inter connecting CdO6 octahedra and SO4 tetrahedra resulting in a framework structure. The mobile Na atoms are present in the framework, resulting in a high ionic conductivity. The conductivity measurement shows two phase transitions one at around 280°C, which was confirmed later from DTA, dielectric relaxation, high temperature powder diffraction and Raman spectroscopy. Chapter 5 describes the structure and in situ phase separation in two different bimetallic sulfates Na2Mn1.167(SO4)2S0.33O1.1672H2O and K4Cd3(SO4)5.3H2O. These compounds were synthesized keeping them as mimics of mineral structures. The structure of Na2Mn1.167(SO4)2S0.33O1.1672H2O is trigonal, space group R . The stiochiometry can be viewed as a combination of Na2Mn(SO4)22H2O resembling the mineral Krohnkite with an additional (Mn0.167S0.333O1.167) motif. On heating the parent compound on the diffractometer to 500K and keeping the capillary at this temperature for one hour, a remarkable structural phase separation occurs with one phase showing a single crystal-single crystal transition and the other generating a polycrystalline phase. The resulting single crystal spots can be indexed in a monoclinic C2/c space group and the structure determination unequivocally suggests the formation of Na2Mn(SO4)2, isostructural to Na2Cd(SO4)z. The mechanism follows the symmetry directed pathway from the rhombohedral → monoclinic symmetry with the removal of symmetry subsequent to the loss of the two coordinated water molecules. In case of K4Cd3(SO4)5.3H2O the structure belongs to the space group P21/n at room temperature and on heating to 500K and holding the capillary at this temperature for 60 minutes as before, the CCD images can be indexed in a cubic P213 space group after the phase separation, generating K2Cd2(SO4)3, belonging to the well known Langbeinite family, while the other phase is expected to be the sought after K2Cd(SO4)2. The possible pathways have been discussed. Chapter 6 reports the charge density studies of phase transitions in a type II langbeinite, Rb2Mn2(SO4)3. The structure displays two different phases, cubic at 200K, orthorhombic at 100K respectively. After multiple refinements it is found that there are significant differences in the actual bond path (Rij) and the conventional bond length. In the cubic phase the distortions in sulfate tetrahedral are more than in the orthorhombic phase which could be the expected driving force for the phase transition to occur. Appendix contains reprints of the work done on the structures of the following: a) Rb2Cd3(SO4)3(OH)2.2H2O: structural stability at 500 K b) Structure of (NH4)2Cd3(SO4)4.5H2O c) Structure of Rb2Cd3(SO4)4.5H2O