Thesis (Ph. D.)--School of Physics, Georgia Institute of Technology, 2004. Directed by Walter A. de Heer. / Vita. Includes bibliographical references (leaves 84-90).

Master of Science / Department of Chemistry / Mark D. Hollingsworth / Most urea inclusion compounds (UICs) are known to share a common packing arrangement in which the urea host forms helical ribbons held together by hydrogen bonds to form a series of linear, hexagonal tunnels. Because UICs can encapsulate a wide variety of linear guest molecules, they serve as useful model systems for probing mechanisms of crystal growth and molecular recognition. In this thesis, the syntheses (or attempts thereof) of six compounds that will serve as consequential guest molecules in studies of UICs are presented. These compounds are (5S,6S)-2,9-decanedione-d2, 1,6-dicyanohexane-1,1,6,6-d4, 1,11-undecanedioic acid, bis(3-oxobutyl) adipate, 2,16-heptadecanedione, and 2-eicosanone. With the exception of (5S,6S)-2,9-decanedione-d2, whose synthesis remains incomplete, detailed synthesis and crystal growth of the UICs of these compounds are discussed. Ongoing studies with the UICs containing these guests include the determination of the absolute configuration of UICs, the study of guest conformer population changes via solid-state NMR, the development and identification of novel ferroelastic UICs, and the classification of guest ordering in a series of alkanedione UICs.

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.

No description available.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Uma parcela significativa da pesquisa cientÃfica hodierna baseia-se na sÃntese, caracterizaÃÃo ou aplicaÃÃo de materiais nanoestruturados. No intuito de possibilitar um maior entendimento das intrigantes propriedades destes materiais, muitas tÃcnicas com resoluÃÃo nanomÃtrica e atà subnanomÃtrica foram criadas nos Ãltimos 50 anos e tÃm passado por um processo de contÃnuo aprimoramento. Apesar do grande desenvolvimento tÃcnico e cientÃfico da instrumentaÃÃo disponÃvel, a caracterizaÃÃo Ãtica com resoluÃÃo nanomÃtrica destes materiais tem se mostrado um desafio para pesquisadores do mundo inteiro. Nesse contexto, as tÃcnicas baseadas em radiaÃÃo de campo prÃximo tÃm despontado como uma boa alternativa para quebra do limite de difraÃÃo, que constitui um limite natural para os instrumentos Ãticos convencionais. AlÃm disso, a microscopia de campo prÃximo em modo de iluminaÃÃo e contato adquire simultaneamente informaÃÃes Ãticas e topogrÃficas do material, o que permite fazer uma distinÃÃo entre as propriedades Ãticas nanomÃtricas reais e as induzidas por topografia. O fenÃmeno de domÃnios cristalogrÃficos tem sido um assunto de interesse da cristalografia desde que ela comeÃou a se desenvolver como ciÃncia. As razÃes Ãbvias para isso sÃo a beleza de formas externas de algumas estruturas de domÃnios, assim como as evidentes e desafiantes relaÃÃes de simetria entre os seus constituintes. Os domÃnios ferroelÃsticos sÃo um dos importantes tipos de domÃnios apresentados por cristais. Tais domÃnios apresentam, algumas vezes, dimensÃes muito reduzidas sem manifestar uma considerÃvel alteraÃÃo na estrutura topogrÃfica da amostra. Por outro lado, o comportamento Ãtico de domÃnios distintos pode ser bem diferente quando sujeitos a uma mesma condiÃÃo de medida. Tais caracterÃsticas tornam esta classe de materiais ideais para um estudo baseado na microscopia de campo prÃximo em modo de iluminaÃÃo e contato. Imagens de domÃnios ferroelÃsticos, utilizando microscopia de campo prÃximo em modo de iluminaÃÃo e contato, foram obtidas com resoluÃÃo nanomÃtrica. Tais imagens, em geral, apresentaram pouquÃssima relaÃÃo com a estrutura topogrÃfica do material, revelando importantes caracterÃsticas Ãticas (ocorrÃncia do efeito de guias de onda nos domÃnios) e estruturais (dimensÃes dos domÃnios ferroelÃsticos, presenÃa de defeitos de deslocamento na rede cristalina). / A significant part of the nowadays scientific research is based on the synthesis, characterization and application of the nanostructured materials. In order to make possible a further understanding of the intriguing properties of these materials, many techniques with nanometric and even subnanometric resolution have been created during the last 50 years and are passing through a process of continuous improvement. In spite of the great scientific and technical development on the available instrumentation, the optical characterization with nanometric resolution of these materials remains a challenge for researchers from all over the world. In this context, techniques based on near field radiation have emerged as a great alternative for the diffraction limit break which is a nature imposed limit for conventional optical instruments. Besides this, contact near field microscopy in illumination mode acquires optical and topographical information of the material simultaneously. This capability permits the distinction between the real and topographic induced nanometric optical features. The domain phenomenon in crystals has been a subject of interest for crystallographers since crystallography started to develop as a scientific branch. The obvious reasons are the beauty of some domain patterns as well as evident and challenging symmetry relations between their constituents. The ferroelastic domains are one of the important kinds of domains presented by crystals. They have, sometimes, very small dimensions without inducing any topographic element on the sample. On the other side the optical behavior of different domains under almost the same measurement condition may be very dissimilar. Such characteristics make then an ideal class of materials for contact near field microscopy in illumination mode based studies. Ferroelastic domains images, using near-field optical microscopy in illumination and contact mode, were obtained with a nanometric resolution. Such images, in general, presented very little relation with the topographical structure of the material, revealing optical and structural features such as occurrence of the waveguide effect in the domains, domainÂs dimensions and presence of dislocations on the crystalline structure.  

DANTAS, Saulo Maia. Microscopia de campo próximo aplicada ao estudo dos domínios ferroelásticos. 2011. 116 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2011. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-10-16T20:43:18Z No. of bitstreams: 1 2011_dis_smdantas.pdf: 2227981 bytes, checksum: 19c007c3550b22fce922a346d6f4508f (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-10-21T20:37:21Z (GMT) No. of bitstreams: 1 2011_dis_smdantas.pdf: 2227981 bytes, checksum: 19c007c3550b22fce922a346d6f4508f (MD5) / Made available in DSpace on 2015-10-21T20:37:21Z (GMT). No. of bitstreams: 1 2011_dis_smdantas.pdf: 2227981 bytes, checksum: 19c007c3550b22fce922a346d6f4508f (MD5) Previous issue date: 2011 / A significant part of the nowadays scientific research is based on the synthesis, characterization and application of the nanostructured materials. In order to make possible a further understanding of the intriguing properties of these materials, many techniques with nanometric and even subnanometric resolution have been created during the last 50 years and are passing through a process of continuous improvement. In spite of the great scientific and technical development on the available instrumentation, the optical characterization with nanometric resolution of these materials remains a challenge for researchers from all over the world. In this context, techniques based on near field radiation have emerged as a great alternative for the diffraction limit break which is a nature imposed limit for conventional optical instruments. Besides this, contact near field microscopy in illumination mode acquires optical and topographical information of the material simultaneously. This capability permits the distinction between the real and topographic induced nanometric optical features. The domain phenomenon in crystals has been a subject of interest for crystallographers since crystallography started to develop as a scientific branch. The obvious reasons are the beauty of some domain patterns as well as evident and challenging symmetry relations between their constituents. The ferroelastic domains are one of the important kinds of domains presented by crystals. They have, sometimes, very small dimensions without inducing any topographic element on the sample. On the other side the optical behavior of different domains under almost the same measurement condition may be very dissimilar. Such characteristics make then an ideal class of materials for contact near field microscopy in illumination mode based studies. Ferroelastic domains images, using near-field optical microscopy in illumination and contact mode, were obtained with a nanometric resolution. Such images, in general, presented very little relation with the topographical structure of the material, revealing optical and structural features such as occurrence of the waveguide effect in the domains, domain´s dimensions and presence of dislocations on the crystalline structure. / Uma parcela significativa da pesquisa científica hodierna baseia-se na síntese, caracterização ou aplicação de materiais nanoestruturados. No intuito de possibilitar um maior entendimento das intrigantes propriedades destes materiais, muitas técnicas com resolução nanométrica e até subnanométrica foram criadas nos últimos 50 anos e têm passado por um processo de contínuo aprimoramento. Apesar do grande desenvolvimento técnico e científico da instrumentação disponível, a caracterização ótica com resolução nanométrica destes materiais tem se mostrado um desafio para pesquisadores do mundo inteiro. Nesse contexto, as técnicas baseadas em radiação de campo próximo têm despontado como uma boa alternativa para quebra do limite de difração, que constitui um limite natural para os instrumentos óticos convencionais. Além disso, a microscopia de campo próximo em modo de iluminação e contato adquire simultaneamente informações óticas e topográficas do material, o que permite fazer uma distinção entre as propriedades óticas nanométricas reais e as induzidas por topografia. O fenômeno de domínios cristalográficos tem sido um assunto de interesse da cristalografia desde que ela começou a se desenvolver como ciência. As razões óbvias para isso são a beleza de formas externas de algumas estruturas de domínios, assim como as evidentes e desafiantes relações de simetria entre os seus constituintes. Os domínios ferroelásticos são um dos importantes tipos de domínios apresentados por cristais. Tais domínios apresentam, algumas vezes, dimensões muito reduzidas sem manifestar uma considerável alteração na estrutura topográfica da amostra. Por outro lado, o comportamento ótico de domínios distintos pode ser bem diferente quando sujeitos a uma mesma condição de medida. Tais características tornam esta classe de materiais ideais para um estudo baseado na microscopia de campo próximo em modo de iluminação e contato. Imagens de domínios ferroelásticos, utilizando microscopia de campo próximo em modo de iluminação e contato, foram obtidas com resolução nanométrica. Tais imagens, em geral, apresentaram pouquíssima relação com a estrutura topográfica do material, revelando importantes características óticas (ocorrência do efeito de guias de onda nos domínios) e estruturais (dimensões dos domínios ferroelásticos, presença de defeitos de deslocamento na rede cristalina).

Dans cette thèse, les interactions magnétoélectriques et optomagnétiques transmises par les contraintes dans les structures ferroélectriques/ferromagnétiques sont étudiées. Nous montrons que la dynamique des déformations du Pb(ZrxTi1-x)O3 aboutit à la manipulation électrique sous-coercitive de multi-états ferroélastiques rémanents. La mesure par une jauge résistive de ces états, ainsi que l'écriture et l'effacement électriques et le stockage ferroélastique, sont démontrés. La configuration des contraintes de matériaux ferroélectriques créée électriquement, permet de modifier l'anisotropie magnétique d'une couche ferromagnétique. Ce phénomène est utilisé pour contrôler le champ magnétique coercitif des composants magnétostrictifs des vannes de spin au moyen des déformations. L’irradiation lumineuse est également utilisée pour entraîner une photostriction rémanente dans le BiFeO3. Cette déformation rémanente est transférée à une couche ferromagnétique et permet un contrôle optique de la coercivité magnétique. Nous montrons comment les états magnétiques peuvent être écrits au moyen de la lumière et effacés par un champ électrique. / In this thesis, the strain-mediated magnetoelectric and optomagnetic interactions in ferroelectric/ferromagnetic structures are studied. The strain dynamics in Pb(ZrxTi1-x)O3 is shown to result in the sub-coercive electrical manipulation of its remanent ferroelastic multi-states. The resistive readout of these states provided by the strain gauge layers, together with the electrically-triggered ferroelastic writing, storage, and erasing, are demonstrated. These strain configurations created by electric fields in ferroelectrics can effectively impact the magnetic anisotropy of a ferromagnetic adlayer. This phenomenon is shown to control the magnetic coercive field of the magnetostrictive components of spin valves via the strain. Light irradiation is shown to result in remanent photostriction effect (photo-driven deformation) in BiFeO3. Such optically-induced remanent deformations can be transferred to a ferromagnetic adlayer and result in the optical control of the magnetic coercive force. It is shown here how magnetic states can be written by light and erased by an electric field.

Les céramiques piézoélectriques, comme le Titatano-Zirconate de Plomb (PZT), peuvent produire une tension électrique quand elles sont soumises à une contrainte mécanique et, inversement, se déforment sous l'effet d'un champ électrique. Ce couplage électromécanique peut être décrit par des équations de comportement linéaires pour des chargements modérés. Cependant, au-delà de certaines valeurs de champ électrique ou de contrainte mécanique, ce couplage devient fortement non linéaire à cause des phénomènes de réorientation de la polarisation électrique. Dans ce travail de thèse, un modèle phénoménologique, qui tient compte des réorientations ferroélectrique (par un champ électrique) et ferroélastique (par une contrainte mécanique) de la polarisation électrique, est proposé. Deux variables internes sont considérées pour décrire l'histoire du chargement et deux surfaces de charges électrique et mécanique sont définies pour déterminer les débuts des écoulements ferroélectrique et ferroélastique. Une version bi-dimensionnelle de ce modèle est développée également pour faire l'étude des structures piézoélectriques minces. Les deux versions 2D et 3D du modèle phénoménologique sont intégrées implicitement en adoptant la méthode de retour radial (prédiction/correction). Deux éléments finis coque et hexaédrique de premier ordre, qui intègrent ce modèle phénoménologique non linéaire, sont ensuite développés et implémentés dans le code de calcul par éléments finis Abaqus via la routine utilisateur UEL (User ELement) / Piezoceramics like lead zirconate titanate or PZT can produce an electric potential when they are subjected to a mechanical stress and deform in the presence of an electric field. This electromechanical coupling can be described by linear constitutive equations for moderate loadings. Nevertheless, this coupling becomes highly non linear when piezoceramics are subjected to high electromechanical loadings due to the electric polarization switching. In this thesis work, a phenomenological material constitutive model that describe the electric polarization ferroelectric switching (by an electric field) and ferroelastic switching (by a mechanical stress) is proposed. To describe the loading history, two internal variables are considered and two electric and mechanical loading surfaces are defined to indicate the onset of domain switchings. A bi-dimensional version of this model is developed to study thin piezoelectric structures. The phenomenological model 2D and 3D versions are implicitly integrated by adopting the return-mapping algorithm. Two shell and hexahedral first-order finite elements are then formulated and implemented into the commercial finite element code Abaqus via the user subroutine UEL (User ELement)