Made available in DSpace on 2014-10-09T12:51:12Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:53Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:27:11Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:37Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

For over half a century, the technological promise of spins manipulable by a small voltage has captivated the interest of experimental and theoretical researchers alike. However, if thin-film multiferroics are to be incorporated into future data storage devices, a much greater understanding of their behaviour and how they differ from their bulk counterparts is required. In this thesis, we probe the fundamental multiferroic properties of BiFeO₃ films through a combination of state-of-the-art diffraction and microscopy techniques. We investigate the coupling between magnetic, ferroelectric, and structural order, with a focus on domains, and how the domain structure may be manipulated in order to tailor the multiferroic properties of the material. Using non-resonant magnetic x-ray scattering (NXMS) and neutron diffraction, we study the magnetic and structural properties of (111)_pc-oriented BiFeO₃ films. Contrary to the general belief that to they grow as a rhombohedral monodomain, we find that they comprise a sub-micron texture of monoclinic domains. The magnetic structure is found to be intimately coupled to the structure, resulting in the propagation vector being locked to the monoclinic b-axis. This magnetoelastic coupling opens up a route to strain-engineer the magnetic domains via epitaxial strain. By growing BiFeO₃ films on a lower-symmetry, TbScO₃ substrate, we are able to engineer a magnetic, structural and ferroelectric monodomain, coherent over the entire film, constituting an increase in the domain size by over five orders of magnitude. We directly demonstrate the coupling between ferroelectric and magnetic order parameters of the cycloidal magnetic structure. Using NXMS polarimetry to measure directly the magnetic polarity, we show that upon switching the ferroelectric polarisation, the magnetic polarity switches accordingly---a major rearrangement of the magnetic structure, with each spin rotating by 90 degrees on average. This goes counter to idea that magnetic and ferroelectric order parameters are only weakly coupled in type-I multiferroics. Finally, using photoemission electron microscopy we are able to directly image the sub-micron magnetostructural domain structure. We further show that there is a strong interfacial coupling between the magnetostructural domains of BiFeO₃ with a ferromagnetic overlayer. The BiFeO₃ domains are found to impose a uniaxial anisotropy in the overlayer, opening up a route to control ferromagnetic domains.

Orientador: Maria Margarita Torres Moreno / Banca: Antenor Zanardo / Banca: Sérgio Ricardo Christofoletti / Resumo: A presente dissertação aborda o estudo de matérias-primas provenientes de três localidades distintas distribuídas entre São Paulo (Mina Tabajara em Limeira e Parque Ouro Fino em Sorocaba) e sul de Minas Gerais (afloramento em Jacuí), pertencentes ao Grupo Itararé/Formação Aquidauana, Permo-Carbonífero da Bacia do Paraná. Com o intuito de aprofundar os conhecimentos sobre matérias-primas cerâmicas, foram determinadas as características químicas, físicas e mineralógicas, ensaios cerâmicos, métodos de controle, petrografia e influência do intemperismo. Os ensaios cerâmicos foram realizados com as matérias-primas de Limeira e de Jacuí. A matéria-prima de Sorocaba foi abordada de outra maneira, não sendo realizados os ensaios cerâmicos devido à quantidade insuficiente de amostra, também não sendo descartada já que litotipos semelhantes podem ocorrer em outros locais. As amostras puras da Mina Tabajara (L1, L2 e L3) não apresentam resultados satisfatórios, porém, os resultados referentes a massa da mistura (LM; 70% de L1, 30% de L2 e 10% de L3), que vem sendo usada nas indústrias da região como massa para correção, pode vir a ser otimizada a nível industrial com o controle adequado da matéria-prima (granulometria e composição principalmente), por exemplo para a produção de peças cerâmicas, em especial rústicas devido a sua coloração avermelhada. Notou-se que uma pequena faixa de variação dentre os materiais da mistura (10% a mais ou a menos) provavelmente não vai causar mudanças significativas na distribuição granulométrica, e por sua vez no empacotamento dos grãos, podendo ser adotada uma tolerância de até 20%. A amostra de Jacuí (J1) é parecida com as da Mina Tabajara quanto à composição química e mineralógica, granulometria e ao grau de intemperismo, e apresenta comportamento semelhante em relação às propriedades cerâmicas... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present thesis is based on the study of raw materials from three different localities distributed between São Paulo (Tabajara Mine - Limeira and Ouro Fino Park - Sorocaba) and southern Minas Gerais (outcrop - Jacuí), all of them belonging to Itararé Group/Aquidauana Formation, Permo-Carboniferous of Paraná Basin. The main objective was to increase knowledge of ceramic raw materials in use or potential, by determining the chemical, physical and mineralogical caractheristics, ceramic tests, control methods, petrography and weathering influence. The ceramic tests were performed with Limeira and Jacuí raw materials. The raw material of Sorocaba was differently approached, ceramic tests weren't made because it occurs within the boundaries of a park, and it was not discarded since similar rocks can occur in other sites. The pure samples of Tabajara Mine (L1, L2 and L3) don't show satisfactory results, however, the results regarding to the mixture mass (LM, 70% of L1, 30% of L2 and 10% of L3), which has been used by the industries in the region as correction mass, could be optimized at an industrial level with the proper control of the raw material (grain size and composition mainly), e.g. for the production of rustic ceramics because of its reddish color. It was noted that a small range of variation among the materials of the mixture (10% more or less) probably won't cause significant changes in particle size distribution, as well as the packaging of grains, and a tolerance of up to 20% may be adopted. The Jacuí (J1) sample is similar to the ones of Tabajara Mine, as to chemical and mineralogical composition, grain size and degree of weathering, presenting similar behavior regarding to the ceramic properties. Factors such as particle size distribution with fine grain predominance, larger cation exchange capacity and specific surface and larger... (Complete abstract click electronic access below) / Mestre

La problématique des condensateurs céramiques à très hautes performances est récurrente dansde nombreux secteurs de l’énergie électrique. Elle prend toute son acuité en microélectronique « nomade», où les circuits doivent être de plus en plus miniaturisés. Ces condensateurs, peuvent occuperjusqu’à 50 % de l’espace sur le circuit imprimé, réduire leurs dimensions devient donc un impératif.Dans ce contexte de nouveaux matériaux à permittivité colossale ont été découverts, commepar exemple CaCu3Ti4O12 (CCTO). Le mécanisme IBLC (Internal Barrier Layer Capacitance),décrivant des grains semi-conducteurs et des joints de grains isolants, permet aujourd’hui d’expliquerces fortes permittivités. Cependant l’origine de la semi-conductivité des grains ainsi quele caractère isolant des joints de grains donne encore matière à controverse. Ce travail a donc undouble objectif, d’une part concevoir un matériau possédant des propriétés diélectriques similairesà CCTO, et d’autre part comprendre les différents mécanismes responsables de ces permittivitésexceptionnelles. La première partie de ce manuscrit présente les caractéristiques d’usages descondensateurs, elle à également pour objectif de lister les mécanismes qui ont été proposés parla communauté scientifique pour tenter d’expliquer la forte permittivité de CCTO. La deuxièmepartie présente d’une part les techniques de caractérisations qui ont été utilisées pour analyserles composés présentés dans ce manuscrit, en insistant plus particulièrement sur la spectroscopied’impédance, largement utilisée dans cette étude. Elle présente d’autre part les techniques de synthèsesqui ont été expérimentées pour synthétiser un nouveau matériau à permittivité colossale :Ba4YMn3O11,5±δ. Les caractérisations structurale et micro-structurale de Ba4YMn3O11,5±δ serontévoquées dans la troisième partie de ce manuscrit. Enfin, les diverses optimisations qui ontété réalisées sur Ba4YMn3O11,5±δ, pour tenter d’améliorer ces propriétés diélectriques, serons évoquées.Nous détaillerons dans cette dernière partie les substitutions ayant été réalisées sur le sitedu baryum et du manganèse, ainsi que la création d’une phase possédant un cation différent del’actuel yttrium et présentant également des propriétés diélectriques très intéressantes. / The problem of ceramic capacitors with very high performance is recurrent in many areas ofElectrical Energy. It takes all its acuteness in « nomadic » microelectronics (cell phone, tablet, mp3player...) where the circuits must be increasingly miniaturized. These capacitors can take up to50 % of the space on the PCB, reducing their size becomes an imperative. In this context newmaterials with colossal permittivity were discovered, such CaCu3Ti4O12 (CCTO). The mechanismIBLC (Internal Barrier Layer Capacitance), describing semiconductor grains and insulating grainboundaries can now explain these high permittivities. However, the origin of the semiconductivitygrains and the insulating character of grain boundaries give even controversial. The aim is thus twofold,on one hand to synthesize a material possessing similar dielectric properties to CCTO, and onthe other hand to understand the various mechanisms responsible for these exceptional permittivity.The first part of this thesis presents various characteristics of capacitors uses, it also aims to listthe mechanisms that have been proposed by the scientific community to try to explain the highpermittivity of CCTO. The second part presents firstly the characterization techniques whichwere used to analyze all the compounds described in this manuscript, with particular emphasison impedance spectroscopy. It presents on the other hand synthesis techniques that have beentried to synthesize a new material with colossal permittivity : Ba4YMn3O11,5±δ. Structural andmicro-structural characterizations of Ba4YMn3O11,5±δ will be discussed in the third part to themanuscript. Finally, the various optimizations that were performed on Ba4YMn3O11,5±δ, to try toimprove the dielectric properties, will be discussed. We detail in this last part substitutions havingbeen made on the site of barium and manganese and the creation of a phase having a differentcation in the present yttrium site and having dielectric properties very interesting also.

Structure of submicrocrystalline materials was investigated by X-ray powder diffraction, mainly by modelling of widths and shapes of diffraction profiles. The diffraction method was applied to colloid gold nanoparticles, copper samples deformed by equal channel angular pressing and titanium dioxide nanoparticles prepared by various chemical routes. Dislocations and twin faults were identified in the metallic samples from characteristic broadening of diffraction lines. Densities of lattice defects were estimated from the diffraction data. Possibilities and limits of the diffraction method for characterisation of a crystallite size distribution were tested on the titanium dioxide samples. Crystallites of size in the range 3-25 nm could be well characterised. The problems were encountered only for samples with extremely broad size dispersion. Diffraction methods and a computer program were developed and tested, which can be applied also for the analysis of thin films.

Real structure of heteroepitaxial GaN and AlGaN layers is studied by diffuse x-ray scattering. A new developed method based on Monte Carlo simulation enabling to determine densities of threading dislocations in c-plane GaN and stacking faults in a-plane GaN is presented. The results of Monte Carlo simulations are compared with ones obtained by use of other conventional techniques. The advantages and limitations of the new method are discussed in detail. The methods accuracy is estimated as about 15%. We have shown that our method is a reliable tool for threading dislocations and stacking faults densities determination.

Cette thèse porte sur l’analyse microstructurale d’intermétalliques formés par réaction à l’état solide entre une couche mince de métal Ni(Co) et un substrat d’InGaAs et s’inscrit dans le cadre du développement de reprises de contact pour les dispositifs MOSFET sub-10 nm ou les applications photoniques. Ce travail comporte une partie relative au développement d’une méthodologie de diffraction des rayons x adaptée à ces composés très texturés et deux parties distinctes où nous décrivons et discutons les résultats expérimentaux.L’étude microstructurale (phase, texture…) des intermétalliques obtenus par réaction à l’état solide est rendue complexe par la formation transitoire de phases métastables, non stœchiométriques parfois, contraintes mécaniquement, et présentant en général des orientations cristallines (texture cristallographique) très marquées. Du fait de cette complexité microstructurale, ces intermétalliques n’ont souvent pas été caractérisés de façon complète et peu de connaissances se trouvent sur leur structure et leur formation. Aussi, et pour caractériser de façon complète et sans omettre des phases ou des orientations dans le système Ni-In-Ga-As, nous avons contribué au développement d’une méthode de mesure globale et rapide par diffraction des rayons X permettant de reconstruire une cartographie large 3D de l’espace réciproque. Les données recueillies par cette méthode sont reconstruites afin d’extraire soit des diagrammes de diffraction dits « détexturés », soit des figures de pôle…permettant une analyse semi quantitative de la microstructure des échantillons.Dans la première partie des résultats expérimentaux, nous nous intéressons à la caractérisation des intermétalliques formés à partir d’empilements Ni/InGaAs/InP recuits ex-situ à différentes températures. Nous décrivons la formation des intermétalliques, leurs textures, et leurs paramètres structuraux. Nous relevons certains aspects de la microstructure qui évoluent en fonction de la température de recuit comme l’anisotropie de texture, la stœchiométrie des intermétalliques et le domaine d’existence thermique et nous proposons des hypothèses qui peuvent expliquer l’évolution de ces phénomènes. Cette première étude faite sur des substrats InP a été confrontée aux résultats obtenus pour des intermétalliques similaires réalisés sur substrats InGaAs/GaAs/Si. En effet, les substrats Si sont les substrats industriellement ciblés pour la réalisation de composés logiques à canal III-V à grande échelle (sur des plaquettes de 300mm de diamètre). Ensuite, nous avons comparé la métallisation de la couche d’InGaAs dans le cas de Ni pur avec la métallisation d’InGaAs lorsqu’un élément d’alliage (Co) est ajouté à la couche de Ni. Ainsi, l’analyse microstructurale révèle des différences notamment sur les textures qui ont été interprétées sur la base de considérations thermodynamiques, mais aussi structurales comme l’alignement des deux couches entre elles, liées à des aspects plus cinétiques.Dans la deuxième partie de ce travail, nous présentons les résultats des analyses in situ effectuées par cartographies de l’espace réciproque en 3D au synchrotron ESRF à Grenoble. Il s’agit de suivre en temps réel par diffraction des rayons X, les réactions à l’état solide des échantillons du type Ni (7 nm et 20 nm)/InGaAs/InP et Ni0.9Co0.1 (20 nm)/InGaAs/InP lors de recuits par rampes... Ensuite, nous avons effectué des recuits isothermes sur les échantillons de type Ni (20 nm)/InGaAs/InP. Ces différentes mesures, couplées avec des hypothèses sur la croissance nous ont permis d’extraire les paramètres cinétiques relatifs à la formation de la première phase d’intermétallique. Les textures observées et leur évolution lors des recuits thermiques in situ sont différents des recuits ex situ. Ceci peut notamment être expliqué par un mode de recuit différent dans le cas in situ où la cinétique du système est plus lente, favorisant ainsi les structures et textures les plus stables. / This thesis focuses on the microstructural analysis of intermetallics formed by solid-state reaction between a thin layer of Ni (Co) metal and an InGaAs substrate and was carried out in the framework of contact development for sub-10 nm MOSFET but have also photonic applications. This work includes a part related to the development of an X-ray diffraction methodology adapted to highly textured compounds and two distinct parts in which we describe and discuss the experimental results.The microstructural study (phase, texture ...) of intermetallics obtained by solid-state reaction is complicated due to the formation of transient metastable, often non-stoichiometric and mechanically stressed phases. These phases have generally very marked crystalline orientations (crystallographic texture). Because of this microstructural complexity, these intermetallic have often been not fully characterized and there is little knowledge about their structure and formation. Moreover, and to fully characterize the Ni-In-Ga-As system without omitting phases or textures, we have contributed to the development of a comprehensive method of rapid measurement by X-ray diffraction to reconstruct large 3D maps of the reciprocal space. The collected data through this method are reconstructed to extract either diffraction diagrams called "detextured" diagrams or pole figures ... which allows a semi-quantitative analysis of the intermetallic microstructure.In the first part of the experimental results, we focus on the characterization of intermetallic formed through Ni / InGaAs / InP stacks and annealed ex situ at different temperatures. We describe the formation of the intermetallics, textures, and structural parameters. We note some aspects which vary depending on the annealing temperature such as the texture anisotropy, the stoichiometry of intermetallic and range of thermal existence and propose hypotheses that can explain the evolution of these phenomena. The studies on InP substrates were compared to results obtained for similar intermetallic made on GaAs / Si substrates. Indeed, the Si substrates are targeted for industrials to achieve logic compounds III-V channel large-scale (on 300 mm wafers). Then, we compared the metallization of the InGaAs layer in the case of pure Ni metallization with the results when an alloying element (cobalt) was added to the Ni layer. The microstructural analysis revealed several differences especially texture differences. These differences were interpreted on the basis of thermodynamic considerations, but also on the basis of structural alignment of the two layers together which are also linked to more kinetic aspects.In the second part of this work, we present the analysis results of studies performed by in situ 3D Reciprocal Space Mapping on the ESRF synchrotron in Grenoble. We followed the formation and stability of the intermetallics by real-time X-ray diffraction measurements, for different kind of samples: Ni (7 nm and 20 nm) / InGaAs / InP and Ni0.9Co0.1 (20nm) / InGaAs / InP, using ramp annealing... Then, we performed isothermal annealings for Ni(20 nm) / InGaAs / InP samples. These measurements, coupled with assumptions on the intermetallic growth, allowed us to extract the kinetic parameters for the formation of the first phase of the intermetallic. The observed textures and their evolution during in situ thermal annealings are different than ex situ annealing. This can be explained by a different mode of annealing in the case of in situ where the kinetics of the system is slower, thus favoring the most stable structures and textures.

This thesis is concerned with the evaluation, in-situ, of the elastic strain energy release rate of cracks. This can define the criteria for crack propagation, and it is usually necessary to obtain this via calculation from the geometry and applied load. A new method is proposed, based on the conjoint use of digital image correlation to measure full-field displacements and finite element to extract the strain energy release rate of surface cracks. It has been extended to 3-D datasets with the use of digital volume correlation and tomographic imaging. A finite element model with imported full-field displacements measured by DIC/DVC acting as boundary conditions is solved and the J-integral is calculated. For linear elastic materials, modal contributions can be separated via the interaction integral. The method has been benchmarked using synthetic datasets to assess its sensitivity to noise and experimental uncertainties. It is very robust to experimental noise and can be used without knowledge of the specimen geometry and applied loads. The application of the method in 2-D is demonstrated in an analysis of experimental data for a mode I fatigue crack, introduced to an aluminium alloy compact tension specimen. Analysis of mixed-mode cracks in 2-D is shown on a PMMA sample with the Arcan geometry. In 3-D, static loading of a fatigue crack in nodular graphite cast iron is studied and the results from the method are compared with those obtained via a field-fitting approach. Diffraction analysis of polycrystalline materials can determine the full tensor of the elastic strains within them. Maps of elastic strains can thus be obtained typically using synchrotron X-rays or neutrons. A method is presented to calculate the elastic strain energy release rate of a crack from 2-D diffraction strain maps. The diffraction data is processed via a finite element approach to obtain the parameters required to calculate the $J$-integral. A validation is presented using a synthetic dataset from a finite element model. Its experimental application is demonstrated in an analysis of synchrotron X-ray diffraction strain maps of a propagating fatigue crack in a bainitic steel, before and after an overload. Finally, a complex case study of stable fracture propagation in polygranular isotropic nuclear graphite is presented. Synchrotron X-ray tomography and strain mapping by diffraction were combined with DVC and image analysis to extract the full-field displacements and elastic crystal strains. The displacement fields have been analysed using the developed methods to extract the critical strain energy release rate for crack propagation. Non-linear properties described the effect of microcracking on the elastic modulus in the fracture process zone. The analysis was verified by comparison of the predicted and measured elastic strain fields.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-26T19:38:51Z No. of bitstreams: 1 POLYANA TARCIANA ARAÚJO DOS SANTOS – TESE (UAEMa) 2015.pdf: 2974694 bytes, checksum: 08e52baa2c42ce5e7b0e35cbf00934bd (MD5) / Made available in DSpace on 2018-06-26T19:38:51Z (GMT). No. of bitstreams: 1 POLYANA TARCIANA ARAÚJO DOS SANTOS – TESE (UAEMa) 2015.pdf: 2974694 bytes, checksum: 08e52baa2c42ce5e7b0e35cbf00934bd (MD5) Previous issue date: 2015-01-29 / CNPq / Neste trabalho de pesquisa foi obtido um material híbrido a base de nanoferritas Ni0,5Zn0,5Fe2O4 e CoFe2O4 modificada a superfície com agente silano e funcionalizadas com quitosana visando seu uso como biossensores. Para este fim, as nanoferritas foram sintetizadas por reação de combustão e silanizadas com o 3-aminopropiltrimetoxissilano. A funcionalização foi realizada pelo método de evaporação do solvente usando o biopolímero quitosana. Todas as amostras foram caracterizadas por difração de raios X, espectrometria de infravermelho por transformada de Fourier, espectroscopia por energia dispersiva de raios X, análise termogravimétrica, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, teste de sedimentação e separação magnética, medidas magnéticas e análise in vitro por citotoxidade. As amostras como sintetizadas apresentaram a formação da fase única do espinélio em estudo com característica nanométrica e após a formação do híbrido a estrutura do material foi mantida. Nos espectros de infravermelho observaram-se bandas de absorção características das nanoferritas e bandas referentes à presença do agente silano e da quitosana. Por meio das micrografias observou-se a formação de aglomerados de aspecto frágil, e após silanização e funcionalização observou-se uma morfologia com aglomerados de aspecto mais rígido constituídos de nanopartículas fortemente ligadas. A análise termogravimétrica mostrou que as nanoferritas apresentaram baixa perda de massa e que após formação do híbrido houve um aumento da perda de massa comprovando assim, a presença do agente silano e da quitosana. Quanto ao comportamento magnético, ambas as nanoferritas apresentaram elevada magnetização de saturação típica de materiais ferrimagnéticos, este comportamento foi mantido após formação do híbrido sendo adequado para aplicações biotecnológicas. A viabilidade celular das nanoferritas mostrou característica citotóxica para a ferrita Ni0,5Zn0,5Fe2O4 e não citotóxica para a ferrita CoFe2O4, a formação do híbrido favoreceu aumento da viabilidade celular em ambas as nanoferritas. Os materiais híbridos obtidos são promissores para o uso na nanobiotecnologia como biossensores e/ou em tratamento como diagnóstico clinico. / In this research was obtained a hybrid material nanoferrit es base Ni0,5Zn0,5Fe2O4 and CoFe2O4 modified the surface with silane agent and functionalized chitosan aiming their use as biosensors. To this end, nanoferritas were synthesized by combustion and silanized with 3-aminopropyltrimethoxysilane. The functionalization was carried out by the solvent evaporation method using the biopolymer chitosan. All samples were characterized by X-ray diffraction, infrared spectroscopy by Fourier transform spectroscopy energy dispersive X-ray, thermal analysis, scanning electron microscopy, transmission electron microscopy, sedimentation test and magnetic separation, magnetic measurements and Analysis by in vitro cytotoxicity. The samples showed synthesized as the formation of spinel single phase with nanometer feature under study and after the formation of the hybrid structure of the material has been maintained. In the infrared spectra there were absorption bands characteristic of nanoferritas and bands related to the presence of the silane agent and chitosan. Through micrographs showed the formation of agglomerates frail and after silanization and functionalization was observed with a morphology more rigid aspect of tightly bound agglomerates of nanoparticles. Thermogravimetric analysis showed that the nanoferritas showed low weight loss and that after hybrid formation was increased mass loss thereby proving the presence of the silane agent and chitosan. As for the magnetic behavior, both nanoferritas had high magnetization typical saturation ferrimagnetic materials, this behavior continued after the hybrid formation is suitable for biotechnological applications. Cell viability nanoferritas showed characteristic for cytotoxic and non-cytotoxic ferrite Ni0,5Zn0,5Fe2O4 to CoFe2O4 ferrite, the formation of hybrid favored increased cell viability in both nanoferritas. The obtained hybrid materials are promising for use in nanobiotechnology as biosensors and / or treatment and clinical diagnosis.