O estudo da eletrorredução de nitrato teve início na década de 70 e o catalisador mais estudado para esta reação é a platina, embora, para fins ambientais, o paládio seja mais indicado por apresentar maior seletividade para a formação de N2. Neste trabalho a eletrorredução de nitrato foi estudada em eletrodos de Pd, Pt e Pt com camadas de Pd. Primeiramente foi feito um estudo com nanopartículas de Pt, Pd e Pt com uma monocamada de Pd dispersas em carbono, mas a dificuldade em sugerir um mecanismo nesse tipo de eletrodo levou à utilização de eletrodos monocristalinos, que tem a superfície conhecida. Foram feitos estudos eletroquímicos em eletrodos de Pd(hkl) que não apresentaram grande atividade frente a redução de nitrato, uma vez que o potencial inferior não foi menor que 0,2 V, para evitar excessiva absorção de hidrogênio. Em Pt(hkl) os resultados obtidos estão de acordo com os publicados na literatura e comprovam a sugestão de que o produto final é NH4 +. Para observar a atividade do paládio frente à reação, foram utilizados eletrodos monocristalinos de Pt (hkl) com multicamadas de paládio, que se comportam como monocristais de paládio, mas sem absorver hidrogênio. Nestes materiais foram feitos estudos eletroquímicos e de FTIR. Verificou-se que a atividade dos eletrodos depende da estrutura e do eletrólito, mas a definição de um mecanismo fica comprometida pelo fato do solvente (H2O ou D2O) favorecer a formação de um produto ou outro, embora tenha sido comprovada a formação de NO(ads) em todos os casos. / The study of nitrate electro-reduction started in the 70s and the most studied catalyst for this reaction is platinum, however because of environmental reasons, palladium is more indicated since it has higher selectivity for the formation of N2. In this work the nitrate electro-reduction was studied on Pd, Pt and Pt modified with Pd layers. First, a study involving carbon-supported nanoparticles of Pt, Pd and Pt with a Pd single layer was carried out, but the difficulty suggesting a reaction mechanism for this kind of electrode has driven to the use of single crystals, because of their defined surface structure. So, electrochemical studies were made on Pd(hkl) electrodes, but these materials did not present great activity for nitrate reduction, because the electrode potential was not decreased below 0,2 V, to avoid large hydrogen absorption. For Pt(hkl) the obtained results are in agreement with those published previously, confirming the suggestion that NH4 + is the final product. To characterize the palladium activity for this reaction, Pt(hkl) single crystals with palladium multilayer were employed, because these materials have a behavior similar to palladium single crystals, but without hydrogen absorption. Electrochemical and FTIR experiments were done to characterize the i vs E responses and to follow the reaction intermediates and products. It was seen that the activity depends on the electrode structure and the electrolyte, but the mechanism determination pointed to a uncertain situation where the solvent (H2O or D2O) drives to the formation of one product or another, although the production of NO(ads) has been observed in all cases.

Organic single crystals are of particular fundamental interest as tools in probing the intrinsic electrical properties and the upper limit of performance for a given organic semiconducting molecule devoid of disorder. Rubrene single crystals are of particular interest in the field of organic electronics due to the high levels of charge carrier mobilities measured in transistors constructed of the same. In this thesis, we explore the properties of rubrene single crystal transistors. The photocurrent properties of rubrene single crystals are measured in ‘air-gap' transistors whose unique structure allows the measurement of photocarrier dynamics without the influence of a dielectric that can act as a source for traps. This structure has allowed us to identify phenomenon like persistent photoconductivity associated with the creation of oxygen related traps on the rubrene surface. Transient studies of the photocurrent reveal the presence of bimolecular recombination of the charge carriers. In addition, we have also performed optical spectroscopy studies including Raman spectra measurements which revealed the presence of endoperoxide related signature on the surface of the crystal while also confirming the low levels of intermolecular coupling present between the molecules. We have also explored the extrinsic factors that determine the surface conductivity of the rubrene crystal, particularly the presence of oxide related compounds on the surface of the crystal using XPS and photoluminescence measurements. The impact of photo-oxidation of the rubrene crystal on the surface conductivities were evaluated by a novel experiment involving the gradual photo-oxidation of the rubrene surface using a focussed laser. The creation of a deep acceptor state that can trap electrons indicates that the electrical properties of the rubrene surface like high unipolar p-type II conductivity and photoconductivity may be modulated by the presence of these oxygen induced states.

Relaxor ferroelectric PZN-xPT and PMN-xPT single crystals exhibit extraordinary electromechanical properties. They are under development for applications in sensors, actuators and transducers. The polarization switching and phase transition behavior of PZN-4.5%PT and PMN-32%PT single crystals under external loading has been investigated. Experimental investigation elucidates the polarization switching and phase transition behavior of relaxor ferroelectric crystals at different orientation cuts under combined temperature, electric field and stress loading. These crystals exhibit strong orientation dependence of electromechanical properties, and the applied fields all affect the poling and phase states of the crystals. Based on experimental investigation, crystal variant modeling was developed to compute the piezoelectric properties of multi-domain crystals at different orientation cuts from a set of properties for the single domain. Thermodynamics and work-energy analysis of field induced phase transitions in these single crystals sheds light on the phase transition mechanism of ferroelectric crystals. Fracture behavior of relaxor single crystals under non-uniform electric fields at a partial electrode edge has also been measured and analyzed.

The chemisorption and anodic oxidation of hydroquinone (H2Q) and benzoquinone (BQ) at palladium electrode surfaces was studied by a combination of electrochemistry (EC), Auger electron spectroscopy (AES), high-resolution electron- energy loss spectroscopy (HREELS) and electrochemical-scanning tunneling microscopy (EC-STM) on a smooth polycrystalline and well-defined (single-crystalline) Pd(100) electrode surface. The results point to the following more critical conclusions: (i) Chemisorption of H2Q from dilute (less than or equal to 0.1 mM) aqueous solutions forms surface- coordinated BQ oriented parallel albeit with a slight tilt. (ii) At high concentrations (greater than or equal to 1mM), chemisorption yields an edge-vertical oriented diphenolic species. (iii) The extent of anodic oxidation of the chemisorbed organic strongly depends upon its initial orientation; only the flat-adsorbed species are oxidized completely to carbon dioxide. (iv) The rate of anodic oxidation is likewise dependent upon the initial adsorbate orientation; the rate for vertically-oriented species is more than twice that of flat- adsorbed species. (v) The chemisorbed species are not oxidized (to the same extent) simultaneously; instead, oxidation occurs one molecule at a time. That is, molecules that survive the anodic oxidation and remain on the surface retain their original identities.

The present research program is a renewed attempt at explaining the transformation mechanisms. The experimental investigations has focused on a model analysis of transformations which occur in single crystals, with stable orientations, i.e. Goss{110}<001> and brass{110}<112>, the deformation is carried out by channel-die compression to simulate the rolling process of thin sheets. Next, the samples were annealed at temperatures of primary recrystallization. The analysis of crystallographic transformations was conducted on metals from a wide spectrum of stacking fault energy: low - Cu-2%Al, average- Cu and Ni to high Al and Al-1%Mn. At work were analyzed the mechanisms controlling the initial stages of recrystallization. Detailed analysis of disorientation across the recrystallization front clearly showed that the initial grain orientations were not accidental. The axes of disorientation in the relationship across the front of recrystallization were near normal in {111} planes, but only sporadically covered with the <111> direction. The distribution of the recrystallization angle rotation in relation to the preferences presented through the formation of two maxima values near 30 ° and 45-55 °.

Dans ce travail, nous avons étudié l’effet des contraintes extérieures et des inhomogénéités locales sur les propriétés diélectriques et structurales des cristaux ferroélectriques- relaxeurs à base de plomb PZN-x%PT avec 0%≤x≤12%. Dans une première partie, nous avons déterminé les propriétés diélectriques et structurales du système PZN-6%PT. Pour l’état vierge, ce composé subit la séquence de transition de phase C  T  R, où C, T et R sont, respectivement, les phases cubique, quadratique et rhomboédrique. En appliquant un champ électrique statique, une phase orthorhombique est induite entre les phases T et R. Dans la deuxième partie, nous avons montré la présence d’une anomalie diélectrique à basse température observée sur le PZN-x%PT avec 0%≤x≤12%. Dans ce domaine de température, l’étude structurale ne montre aucune transition de phase. L’ensemble de ces résultats sont interprétés moyennant un modèle basé sur la présence des nano-régions polaires. En troisième partie nous avons déterminé les propriétés diélectriques et piézoélectrique du PZN-12%PT dopé au manganèse dans son état monodomaine. Le dopage affecte, principalement, la permittivité transverse et le coefficient piézoélectrique de cisaillement. Le dopage induit aussi la stabilité de la structure monodomaine et l’effet de mémoire de la microstructure. Ces résultats sont expliqués en utilisant le modèle de symétrie des défauts. Dans la dernière partie, nous nous sommes intéressés à la simulation de l’effet de la présence des dipôles-défaut (dopage) sur les propriétés physiques de BaTiO3. Nous avons mis en évidence l’induction d’un champ électrique interne responsable du décalage du cycle d’hystérésis vers les champs électriques négatifs. / In this work, we studied the effect of external constraints and local inhomogeneities on dielectric and structural properties of the lead-based ferroelectric-relaxor system PZN-x%PT with 0%≤x≤12%. In the first part, we determined phase transformations of [001], [110] and [111] oriented PZN-6%PT single crystals. The un-poled samples undergo C  T  R, phase transitions sequence, where C, T and R, and are rhombohedral, tetragonal and cubic phases, respectively. Under electric field, an intermediate orthorhombic phase is induced between T and R phases. The second part was devoted to the study of the electromechanical and structural properties at cryogenic temperature of the PZN-x%PT system (0%≤x≤12%.). These characterizations show the presence of a dielectric anomaly at low temperatures. In the same temperature range, the structural study does not show any phase transition. These behaviors are interpreted through a model based on the presence of polar nano-regions. In the third part we study the influence of manganese doping on the electromechanical properties of PZN-12%PT single crystal in a single domain state. Doping leads to a decrease of the dielectric transverse permittivity  T 11 and of the shear piezoelectric coefficient d15. This intrinsic effect is discussed by using a volume effect model based on the symmetry conforming principle of point defects. This model explains also the stability of the single domain structure and the memory effect observed during this work. In the last part, we simulated, using molecular dynamics method, the effect of doping (defects-dipoles) on the physical properties of BaTiO3. The introducing of defects-dipoles induces an internal electric field, responsible for the shift of the hysteresis loop.

Este trabalho tem por objetivo principal a caracterização dos microcristais de niobato de lítio (LiNbO3) dopados com óxido de cromo (CrO3) e com óxido de ferro (Fe2O3), crescidos no Departamento de Física e Ciências dos Materiais do Instituto de Física e Química de São Carlos - USP. Para isso, utilizamos as seguintes técnicas: Ataque Químico Preferncial, Ressonância Paragnética Eletrônica (RPE), Absorção Ótica no Visível e Infravermelho Próximo e a Técnica Holográfica. Através da técnica de ataque químico preferencial os domínios ferroelétricos destes cristais foram observados. Os possíveis sítios que os íons Cr3+ e os íons Fe3+ ocupam na rede do LiNbO3 foram estudados por RPE, e os resultados obtidos indicam que o íon Cr3+ ocupa preferencialmente as vacâncias estruturais, enquanto os íons Fe3+ ocupam o sítio do nióbio ou do lítio. O efeito de tratamentos térmicos em atmosferas redutoras e oxidantes sobre a concentração dos íons Fe3+, Fe2+ e dos centros OH-, foram estudados através das técnicas de RPE, absorção ótica no visível e no infravermelho. Através da técnica holográfica, foram observadas altas eficiências de difração holográficas em cristais dopados com ferro. Foram feitas também medidas da variação temporal desta eficiência em cristais tratados e não tratados termicamente, e em alguns casos o efeito de acoplamento de ondas foi observado. / The present work shows the characterization of the lithium niobate (LiNbO3) doped with chromium oxide and iron oxide. Those crystals were grown in the Departamento de Física e Ciência dos Materiais - IFQSC - USP São Carlos. Several experimental techniques were applied like Preferential Chemical Etching, Electron Paramagnetic Resonance (EPR), Near Infrared and Visible Optical Absorption and the Holagraphic Technique. Through the preferential chemical etching we observed the ferroelectric domains. The probable Cr3+ and Fe3+ ion site were studied with EPR, it shows the Cr3+ ions fill possibly structural vacancies, while the Fe3+ ions possibly take place on Li1+ or Nb5+ substitucionally. The thermal treatment effects at reducing and oxidizing atmospheres under several Fe3+, Fe2+ and OH- concentration were studied through EPR, visible and near infrared optical absorption. By using the holographic technique we observed holographic diffraction highly efficient in iron doped crystals. Also were made time dependence efficiency at thermally treated and non treated samples, and in some cases we observed wave coupling effect.

A ênfase de todo o trabalho é relacionada com a preparação de soluções sólidas, concentrando-se na matriz de niobato de lítio, LiNbO3, puro e suas soluções sólidas óxidas, onde obtemos monocristais de LiNbO3 com Cr3+, Fe3+ e Mg2+. Os monocristais de LiNbO3são obtidos pelo método de Czochralski (fusão) e a caracterização de suas propriedades está voltada para a análise da perfeição estrutural, da distribuição de dopantes na matriz cristalina, da orientação dos domínios de dipolos ferroelétricos e o estudo do comportamento do coeficiente de segregação efetivo com os parâmetros de crescimento, com a cinética de adsorção e com o efeito de facetamento / The emphasis of all this work is related to the preparation of solid solutions, concentrating on lithium niobate single crystals, LiNbO3, pure and its oxide solid solutions, where we can obtain LiNbO3 single crystals doped with Cr3+, Fe3+ and Mg2+. The LiNbO3 single crystals are obtained by the Czochralski method (fusion) and the characterization of its properties is on the analysis of the structural perfection, of the distribution of the doping in the crystal matrix, of the orientation of the domains ferroelectrics dipoles and the study of the effective segregation coefficient behavior, with the growing parameters, with the adsorption kinetic and the facet effect

Orientadores: Pascoal José Giglio Pagliuso, Oscar Ferreira de Lima / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-17T19:19:42Z (GMT). No. of bitstreams: 1 Garitezi_ThalesMacedo_M.pdf: 5487109 bytes, checksum: 11408acef0a6ff80a1788db976f23149 (MD5) Previous issue date: 2011 / Resumo: Os supercondutores à base de ferro e arsênico foram descobertos em 2008, primeiramente na forma de um óxido LaFeAsO1-xFx com uma temperatura crítica de 26 K, e poucos meses depois na forma do intermetálico livre de oxigênio Ba1-xKxFe2As2 com Tc = 41 K. Desde então, esses materiais despertaram grande interesse da comunidade cientíca em busca do entendimento da natureza microscópica e da origem da supercondutividade nesses compostos, e sua possível relação com a supercondutividade dos cupratos e dos férmions pesados, onde acreditase que mecanismo de pareamento seja através de flutuações magnéticas. Muitos acreditam que essa nova família de materiais se constituirá na segunda classe de supercondutores de alta temperatura crítica descoberta desde dos cupratos há 30 anos atrás. Por supostamente compartilharem o mesmo mecanismo de supercondutividade dos cupratos, há grande perspectiva de descoberta de compostos a base de Fe-As com altas Tc (apresentam no momento Tcs tão altas quanto 55 K). Além do mais, muitos compostos desta família estudados até então podem apresentar altas correntes críticas comparáveis com supercondutores convencionais utilizados em magnetos comerciais, o que revela o potencial desses materiais para aplicação em fios de transmissão supercondutores e magnetos de alto campo, em especial no caso dos compostos intermetálicos, por serem, a princípio, mais fáceis de se manipular e mais estáveis do que os óxidos cerâmicos. Inicialmente, monocristais da família dos compostos à base de FeAs intermetálicos (Ba1-xKx-Fe2As2, BaFe2-xCoxAs2, etc) foram sintetizados utilizando-se fluxo de Sn. Os monocristais crescido por esse método possuem em média excelentes dimensões (5 mm x 5 mm x 2 mm), mas os estudos mostraram que há uma significativa incorporação substitucional de Sn, o que altera as propriedades microscópicas dos compostos. Atualmente, monocristais dessa família são sintetizados com a técnica de auto-fluxo, que usa excesso de ferro e arsênico para o crescimento. Porém, os monocristais crescidos por esse método têm dimensões cerca de 10 vezes menores e este excesso de reagentes no fluxo que fazem parte do composto pode levar a um desbalanço na estequiometria do material, e isso pode alterar fortemente medidas que sondem propriedades microscópicas, como a simetria do estado supercondutor, por exemplo. Além do mais, o excesso de arsênico traz um perigo adicional para o crescedor. Portanto, é desejável a busca de métodos alternativos de crescimento desses materiais que possam gerar amostras de boa qualidade que permitam um estudo confiável de suas propriedades microscópicas. Nesta dissertação, é apresentado o processo de síntese e caracterização de monocristais da série BaFe2-xCoxAs2 crescida com a técnica de fluxo metálico com um fluxo alternativo, o In. Os cristais sintetizados por esta técnica tiveram suas propriedades macroscópicas, como resistividade elétrica DC (p), susceptibilidade magnética DC (x), calor específico à pressão constante (Cp) e difração de raios-X medidas, e delas foram extraídas as temperaturas de transição magnética e supercondutora, o que permitiu a construção do diagrama de fases temperatura versus composição para esta série. O diagrama obtido neste trabalho está de acordo com o diagrama publicado para amostras crescidas com auto-fluxo, atestando o sucesso do crescimento sistemático dessa série com o fluxo de índio sem prejuízo às suas propriedades macroscópicas. Medidas preliminares de NMR sugerem que as amostras crescidas por fluxo de In têm qualidade cristalina superior às das amostras crescidas por auto-fluxo / Abstract: Iron arsenide based superconductors were discovered in 2008, first in the oxide form in LaFeAs-O1-xFx, which had Tc = 26 K; and a few months later in the intermetallic form, in an oxygen-free compound, Ba1-xKxFe2As2, with a critical temperature of ~ 41 K. They are supposedly the second class of unconventional high temperature superconductors since the discover of Cu-based oxides almost 30 years ago. For being considered similar to the cuprates, and having Tcs as high as 55 K and critical currents of the order of those conventional superconductors used in commercial magnets, these materials have great potential to be used in transmission lines and high field magnetsm, specially in the intermetallic from, since they tend to be, presumably, more flexible and easier to manipulate and stabilize than an oxide ceramic. Furthermore, there is great interest in studying the microscopic nature and the origin of superconductivity in these materials and its relation with magnetism. As of today, single crystals of this family are synthesized mainly with the self-flux technique, which uses excess iron and arsenic in the growth. Yet, this excess of reagents needed to grow these impurity-free crystals can lead to an outbalance of the material's stoichiometry, and that can strongly alter the outcome of experiments which probe microscopic properties such as the symmetry of the superconductor state. Also, the excess of As in the growth is an extra danger for the grower. As such, search for alternative methods of synthesis of these materials is highly desirable. In this work, it's presented the synthesis method and characterization of the BaFe2-xCoxAs2 series grown from In flux. The macroscopic physcial properties such as DC resistivitity (p), DC magnetic susceptibility (x), specific heat at constant pressure (Cp) and X-ray powder diffraction were measured on the In-flux prepared single crystals. From our results, We extracted the magnetic and superconducting transition temperatures which allow us the construction of a temperature composition phase diagram for this series. The obtained phase diagram is in agreement with the diagram constructed using samples grown by the self-flux method, attesting the success of our systematic growth using the In flux without any effect in the macroscopic properties of the crystals. Furthermore, preliminary NMR experiments suggest that the In-grown crystals may be of higher quality than the self-flux grown single crystals / Mestrado / Supercondutividade / Mestre em Física

Neste trabalho crescemos monocristais de Bi12SiO20 (BSO) e de Bi12TiO20 (BTO). Os cristais de BSO foram crescidos pela técnica de Czochralski a partir da fase líquida com composição molar 6Bi2O3:1SiO2. Os melhores resultados foram obtidos para taxas de puxamento entre 1 e 2,5mm/h, a velocidade de rotação foi mantida constante em 20rpm. Os cristais de BTO foram crescidos pelo método top-seeded solution Growth (TSSG) a partir da composição molar 10Bi2O3:1SiO2, com taxas de puxamento menores que 0,3mm/h e velocidade de rotação entre 16 e 30 rpm. A qualidade dos cristais foi avaliada utilizando microscopia óptica e eletrônica, corrosão seletiva e raios-x. Por microscopia óptica identificamos os defeitos macroscópicos e discutimos sua natureza e possíveis causas. Utilizando a técnica de ataque químico seletivo, analisamos a morfologia das figuras de ataque e estimamos a densidade de deslocações. Visando identificar defeitos de estequiometria, fizemos medidas de composição por microanálise eletrônica. Para a caracterização cristalográfica, calculamos o parâmetro de rede por difração de raios-x usando o método do pó e confirmamos a estrutura cristalográfica através do método de Rietveld. E, ainda, medimos a atividade óptica que é uma constante característica dos cristais. / In this work we grew Bi12SiO20 (BSO) and Bi12TiO20 single crystals. The BSO crystals have been grown from the melt composition of 6Bi2O3:1SiO2 by the Czochralski method. The best results were obtained at pulling rates from 1 to 2.5m/h, the rotation rate of 20rpm was constant. The BTO crystals have been grown by the top-seeded solution growth technique from a 10Bi2O3:1SiO2 solution with pulling rates less than 0.3mm/h and rotation rates from 16 to 30rpm. The crystal quality was examined by optical and scanning electron microscopy, selective etching, and x-ray diffraction. We identified the macroscopic defects by optical microscopy and discussed their nature and probable origin. Using selective etching, we analyzed the etching pits morphology and evaluated the dislocation density. To identify stoichiometric defects, composition measurements by electron probe microanalysis were made. To obtain crystallographic characterization, we calculated the cell parameter by powder method x-ray diffraction and used the Rietveld method to verify the crystallographic structure. And, also, we measured the optical activity, a constant of the crystals.