Compostos intercalados de lítio sac considerados materiais apropriados para eletrodos de baterias recarregáveis de lítio. O conhecimento das taxas de difusão, assim como os mecanismos relacionados com a mobilidade dos íons nos espaços interlaminares são portanto pertinentes para a caracterização das propriedades deste tipo de compostos. Investigações por ressonância magnética nuclear tem um papel ativo no estudo do comportamento dinâmico e estrutural destes compostos de lítio sólidos. Por essa razão este trabalho e baseado nos espectros de RMN obtidos entre 150K e 400K em um campo de 2T. As larguras de linha do 1H e do Li+ foram medidas a partir da transformada de Fourier dos FIDs resultantes da excitação da amostra por um pulse &#960/2. O desacoplamento de 1H foi utilizado, quando necessário, para excluir a contribuição dipolar magnética a destes núcleos a largura de linha do 7Li. Os tempos de relaxação spin-rede para os núcleos 7Li e 1H foram obtidos utilizando-se o método de inversão-recuperação. A partir destas medidas, diversos parâmetros dinâmicos e estruturais destes compostos foram encontrados como: energias de ativação, tempos de correlação e coeficientes de difusão dos íons lítio. / Lithium intercalation compounds are considered suitable materials for electrodes in rechargeable lithium batteries. The knowledge of diffusion rates as well as of mechanistic features related with the mobility of ions in the interlamellar spaces is therefore relevant for the regulation of the properties of this kind of compounds. Nuclear magnetic resonance investigations have played an active role in the study of the dynamic and structural behavior of these solid lithium compounds. For this reason this work is based on NMR spectra recorded between 150K and 400K at 2T. The 1H and Li+ linewidths were measured from the Fourier transform of the FIDs following a &#960/2 excitation. IH decoupling was used, when necessary, to exclude the magnetic dipolar contribution of this nucleus to the 7Li linewidth. The 7Li and 1H spin-lattice relaxation time T1 were measured using the inversion-recovery method. Several dynamic and structural NMR parameters were obtained from these NMR measurements like activation energies, correlation times and diffusion coefficients.

Duas famílias de híbridos orgânico-inorgânicos que exibem propriedades de condução iônica, chamados \"ORMOLYTES (organically modified electrolytes)\", foram preparadas pelo processo de Sol-Gel. A Família I foi preparada de uma mistura de 3-Isocianatopropiltrietoxisilano (IsoTrEOS), 0,0\' Bis (2-aminopropil) polietilenoglicol e sais de lítio. Estes materiais apresentam ligações químicas entre as fases orgânica (polímero) e inorgânica (sílica). A Família II foi preparada pelo método de ultra-som de uma mistura de tetraetoxisilano (TEOS), polietilenoglicol e sais de lítio. As fase orgânica e inorgânica não estão quimicamente ligadas nestas amostras. Também foram preparados os polímeros iônicos convencionais poli ( óxido propileno) (PPO) complexados com dois sais diferentes: LiClO4 and LiBF4. A condutividade iônica &#963 do Li+ nestes materiais foram estudadas pela espectroscopia de impedância AC. Valores acima de 10-4 ohm-1.cm-1 foram encontrados à temperatura ambiente. Suas propriedades dinâmicas e estruturais foram estudadas utilizando-se Espectroscopia de Alta Resolução Multinuc1ear em Sólidos por RMN de 1H, 7Li, 13C, 29Si em função da temperatura, -100&#176C e 90&#176C. Um estudo sistemático de RMN foi feito mudando-se a concentração de lítio, o tamanho da cadeia polimérica e a razão em massa polímero/sílica. A estrutura e as propriedades de condução iônicas de ambas famílias foram comparadas com ênfase sobre a natureza das ligações entre as componentes orgânica e inorgânica. Estudos similares de RMN, mudando-se a concentração de lítio e de sal foram feitas para o PPO / Two families of hybrid organic-inorganic composites exhibiting ionic conduction properties, called ORMOLYTES (organically modified electrolytes), have been prepared by the sol-gel process. The family l has been prepared from mixture of 3-isocyanatopropy1triethoxysilane (IsoTrEOS), 0,0\' Bis (2-aminopropyl)polyethyleneglycol and lithium salt. These materiaIs present chemical bonds between the organic (polymer) and the inorganic (silica) phases. The family II has been prepared by ultrasonic method from a mixture of tetraethoxysilane (TEOS), polyethyleneglycol and lithium salt. The organic and inorganic phases are not chemical1ybonded in these samples. It has been also prepared the conventional ionic conducting polymers poly(propylene-oxide) (PPO) complexed with two different salts: LiClO4 and LiBF4. The Lt ionic conductivity (J of these materials has been studied by AC impedance spectroscopy. Values of &#963 up to 10-4 ohm-1.cm-1 have been found at room temperature. Their dynamic and structural properties have been studied using solid-state high-resolution NMR measurements of 1H, 7Li, 13C, 29Si nuclei as a function of the temperature, between 100&#176C and 90&#176C. A systematic NMR study has been done changing the lithium concentration, the polymer chain length and the polymer to silica weight ratio. The structures and the ionic conduction properties of both families were compared with emphasis on the nature of the bonds between the organic and inorganic components. Similar NMR study, changing the lithium concentration and the salt has been done for PPO

Orientador: Eduardo Augusto Ostergren / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Artes / Made available in DSpace on 2018-08-21T16:05:28Z (GMT). No. of bitstreams: 1 Gomes_HermesCoelho_D.pdf: 5719814 bytes, checksum: 274cc851402575712e732dd571aad832 (MD5) Previous issue date: 2012 / Resumo: O presente trabalho tem como proposta uma reflexão sobre a atuação do regente orquestral neste início do século XXI. Podemos observar que, no exercício da função, sob o ponto de vista pragmático, há uma série de atributos que são pré-requisitos essenciais para quem deseja ter domínio sobre esta arte e exercê-la com conhecimento e seriedade. O estudo aponta uma direção construtiva no sentido de conduzir o regente a refletir tanto no aspecto técnico da sua arte, na busca da sonoridade orquestral, quanto nos aspectos do seu cotidiano inerentes no desempenhar de sua função. No primeiro capitulo apresentamos uma visão histórica das atividades próprias ao cargo e sua evolução ao longo do tempo. No segundo, um estudo direcionado ao aspecto técnico da regência e de sonoridade de uma orquestra. No terceiro são abordadas questões relativas à sua contribuição para o desenvolvimento progressivo e aprimoramento da plateia ao levar conhecimento e estimular reflexões que conduzam o público a uma apreciação mais atenta e aprofundada da música sinfônica. Por último são abordados aspectos relacionados à parte administrativa enquanto na direção da orquestra, especificando problemáticas ligadas à gestão de pessoal, à produção de concertos, à captação de recursos e à sua contribuição para a melhora da qualidade de vida da comunidade em que a orquestra está inserida / Abstract: It is the aim of the present work to propose a reflection on the role of the orchestral conductor at the beginning of this XXI Century. One can observe that, from a pragmatic standpoint there are a series of attributes and pre-requisites for the exercise of this activity much essential for those that wish to learn the practice of this form of art with knowledge and seriousness. This study points the way in a constructive direction so to lead the conductor to reflect on the many different aspects of this art be it technical, the search for the orchestral sonority, or elements of his daily routine, all inherent in the exercise of his job. In the first chapter the author presents a historical perspective and its evolution throughout time of the many activities involved in the position of the conductor. The second discusses the technical elements of conducting and the orchestral sound palette. In the third the author elaborates on the many questions related to the conductor's role in audience development, the sharing of his knowledge to stimulate people's participation leading to a more attentive and a deeper appreciation for symphonic music. Finally items pertaining to the artistic administrative area are discussed, more specifically personnel management, concert production, fundraising and the conductor's involvement in social and artistic affairs and his contribution toward a better quality of life in the community in which the orchestra is inserted / Doutorado / Praticas Interpretativas / Doutor em Música

L'analyse de COV spécifiques dans l'haleine (identifié comme biomarqueurs de maladies telles que lecancer) donne une idée de l’activité métabolique et physiologique d'un individu et peut fournir undiagnostic anticipé non-invasif et potentiellement peu coûteux de plusieurs maladies dont le cancer.Mais avant que des tests médicaux ne puissent devenir une réalité clinique, il est nécessaire dedévelopper une technique d’analyse rapide, fiable, économique et portable. Les réseaux de senseurs(nez électroniques) à base de nanomatériaux qui peuvent satisfaire toutes ces exigences, constituentl’élément clef de l'identification des maladies par leur empreinte de COV dans l'haleine. L'objectif decette thèse est de fabriquer différents senseurs chemo-résistifs à base de nanocomposites conducteursayant la capacité de discriminer un ensemble de maladies (comme le cancer du poumon) par l’analysede leur biomarqueur (COV). Par conséquent, afin de fabriquer des senseurs de haute performance avecune grande sensibilité (ppb) et une sélectivité adaptée aux COV ciblés, différentes méthodologiesd’élaboration de nanocomposites conducteur, ont été implémentées. Des fonctionnalisations covalenteset non-covalentes de ces nanomatériaux de carbone ont été réalisées avec différents types demolécules, i.e., oligomères, polymères ou minérales afin d’ajuster la sélectivité et la sensibilité descapteurs. La nanodéconnection des jonctions du réseau percolé formé par les nanocharges de carbone aainsi pu être contrôlée en faisant varier la fonctionnalité chimique de leur surface. Finalement unensemble de senseurs de vapeur chemorésistifs de hautes performances, ayant une sélectivité pour lesbiomarqueurs du cancer du poumon ont pu être fabriqués et intégrés avec succès dans un nezélectronique.The / The analysis of specific VOC in exhaled breath (identified as biomarkers of specific disease like cancer)give an idea of metabolic and physiological activities of an individual and can provide non-invasive andpotentially inexpensive anticipated diagnosis of several diseases including cancer. The invention of afast, reliable, economic and portable technique is highly required before breath testing become a clinicalreality. Nanomaterial based sensor arrays can fulfill all these requirements and can form a solidfoundation for identification of disease related VOC patterns in exhaled breath. The objective of thisthesis was to fabricate different chemo-resistive sensors based on conductive nanocomposites withability to differentiate and discriminate a set of disease (such as lung cancer) biomarker VOC. Thereforein order to fabricate high performance sensors with high sensitivity and required selectivity towardstargeted VOC, adoption of different methodologies for the synthesis of conductive nanocomposite, wasstrongly emphasized.Covalent and noncovalent functionalizations of these carbon nanomaterials with various oligomeric,polymeric or inorganic molecules were done in order to tune the sensor’s selectivity and sensitivity.Nanoswitching at the junctions of percolated network formed by the carbon nanomaterials could becontrolled by varying the organic functionality on the surface.Finally a set of high performance chemoresistive vapour sensors, with different selectivity towardstargeted lung cancer VOC could be fabricated and successfully integrated in an e-nose with highefficiency towards detection and discrimination of a set of disease specific VOC biomarkers.

[pt] As linhas de transmissão têm um papel fundamental no funcionamento do sistema elétrico, efetuando a ligação entre as usinas geradoras e os centros de carga. Quando o sistema de transmissão atinge sua capacidade limite de transferência de potência torna-se necessário expandir o sistema, quer construindo novas linhas quer aumentando a capacidade das existentes. Entre os fatores que limitam a capacidade de transporte de uma linha destaca-se a sua temperatura limite de operação, estabelecida por questões econômicas e de segurança. Pela sua extensão geográfica, a construção de uma linha de transmissão envolve tanto um custo quanto um impacto ambiental elevados. Por estes motivos a recapacitação de linhas existentes, no sentido de aumentar sua capacidade de transporte, tornou-se um assunto prioritário e uma opção estratégica para expansão do sistema elétrico. Neste trabalho analisa-se o problema da temperatura de operação dos condutores de linhas aéreas de transmissão. Descreve-se a metodologia atualmente utilizada para definir o limite operativo das linhas, destacando-se a possibilidade de aumentar sua capacidade limite pelo conhecimento mais preciso da temperatura de operação dos seus condutores.Descreve-se o desenvolvimento de uma série de dois modelos para previsão da temperatura de operação de condutores, um modelo completo, baseado em previsões das diversas variáveis meteorológicas e um modelo direto de previsão que utiliza as séries de valores de temperatura. No desenvolvimento dos modelos de previsão foram utilizados modelos estocásticos, lineares, de amortecimento exponencial e Box-Jenkins e técnicas de Redes Neurais Artificiais. Apresenta-se uma série de testes de validação, que mostram um desempenho muito bom dos métodos de previsão, e ilustra-se as possibilidades de aplicação dos modelos desenvolvidos. / [en] Transmission lines have a fundamental role in the electric system performance,connecting power sources to load centers. When the transmission system attains it`s transmission capability limit, the system must be expanded, either constructing new lines, or upgrading existing ones. Among the factors that can limit a transmission line transfer capability is the operating temperature limit, established for both economic and safety reasons. Due to its geographic extension the construction of a transmission line involves a big economic as well as environmental cost. For this reasons the upgrade of existing lines, in the sense of increasing it`s transmission capability, has become a priority to electric utilities and a main option for system expansion. In this work the problem of transmission line conductors` operational temperature is analised and the methodology presently used to establish it`s operational limit is described. Two models to forecast transmission line conductors` temperature are developped:a complete model which uses forecasts of the relevant metheorological variables,and a direct model using univariate methods on temperature series. In the development of forecasting models, linear stochastic methods such as exponential smoothing and Box-Jenkins, as well as Artificial Neural Networks techniques were used.Finally model validation is presented, showing very good performance of the proposed forecasting models, and some potential applications are suggested.

No description available.

Ce travail de thèse explore la capacité des ligands anilates d’être employés pour la préparation de nouveaux matériaux moléculaires fonctionnels avec des propriétés magnétiques et de conduction électrique. Les anilates, qui sont les dérivés du 2,5-dihydroxy-1,4- benzoquinone substitués sur les positions 3 et 6, ont été sélectionnés comme ligands puisque leurs caractéristiques électroniques et structurales, leurs modalités de coordination et leur capacité de médiation des interactions de super-échange magnétique en font d’excellents ligands pour la préparation de ces matériaux. Plusieurs ligands anilates ont été utilisés pour le design et la préparation d'une nouvelle classe de complexes paramagnétiques octaédriques tris-chélates de formule générale [MIII(X2An)3]3- (MIII = Cr, Fe; X = Cl, Br, I, H, Cl/CN, An = C6O4 2- = anilate). Ces complexes métalliques paramagnétiques ont été complètement caractérisés et utilisés comme briques moléculaires pour la préparation de i) une nouvelle classe de ferriaimants moléculaires, dans laquelle la modification des substituants sur le ligand permet de modifier les interactions entre les centres métalliques, et, par conséquent, les propriétés magnétiques, ii) des conducteurs paramagnétiques moléculaires obtenus par combinaison avec le donneur organique BEDT-TTF, iii) une série de conducteurs moléculaires chiraux obtenus par combinaison du donneur organique TM-BEDT-TTF avec des couches hétéro-bimétalliques anioniques obtenues par association in situ de complexes tris(chloranilate)ferrate(III) et des ions potassium. En outre, ont été synthétisés de nouveaux dérivés anilates avec des propriétés electroactives et de luminescence, afin de démontrer la capacité du motif anilate d’être fonctionnalisé avec différents substituants comme porteurs de propriétés physiques spécifiques. / This work explores the potential of anilate-based ligands in the synthesis of new rational designed functional molecular materials exhibiting improved magnetic and conducting properties. Anilates, namely 3,6-disubstitued 2,5-dihyroxy-1,4- benzoquinones in their dianionic form, have been selected as ligands since their electronic/structural features, coordination modes and ability to mediate magnetic exchange interactions between coordinated metal centers make them potential candidates for the preparation of theabove-mentioned materials. Various anilate derivatives have been used for the preparation of a family of rationally designed tris-chelated octahedral paramagnetic metal complexes of general formula [MIII(X2An)3]3- (MIII = Cr, Fe; X = Cl, Br, I, H, Cl/CN, An = C6O4 2- = anilate). These paramagnetic metal complexes have been thoroughly characterized and used, in turn, as molecular building blocks for the preparation of i) a family of molecule-based magnets, where subtle changes in the nature of the substituents on the anilate moiety were employed as “adjusting screws” in tuning the magnitude of the magnetic interaction between the metals, and thus, the magnetic properties, ii) hybrid paramagnetic molecular conductors in combination with the BEDT-TTF organic donor, iii) a complete series of isostructural chiral molecular conductors obtained by combining the TMBEDT- TTF chiral donor with 2D heterobimetallic anionic layers obtained in situ by the self-assembling of tris (chloranilato)ferrate(III) metal complexes and potassium cations.Moreover, novel anilate derivatives showing electroactive and luminescent properties have been further synthesized, highlighting the versatility of the anilate moiety to be functionalized with suitable substituents carrying selected physical properties.

abstract: Within the past two decades, metasurfaces, with their unique ability to tailor the wavefront, have attracted scientific attention. Along with many other research areas, RADAR cross-section (RCS)-reduction techniques have also benefited from metasurface technology. In this dissertation, a novel technique to synthesize the RCS-reduction metasurfaces is presented. This technique unifies the two most widely studied and two well-established modern RCS-reduction methods: checkerboard RCS-reduction andgradient-index RCS-reduction. It also overcomes the limitations associated with these RCS-reduction methods. It synthesizes the RCS-reduction metasurfaces, which can be juxtaposed with almost any existing metasurface, to reduce its RCS. The proposed technique is fundamentally based on scattering cancellation. Finally, an example of the RCS-reduction metasurface has been synthesized and introduced to reduce the RCS of an existing high-gain metasurface ground plane. After that, various ways of obtaining ultrabroadband RCS-reduction using the same technique are proposed, which overcome the fundamental limitation of the conventional checkerboard metasurfaces, where the reflection phase difference of (180+-37) degrees is required to achieve 10-dB RCS reduction. First, the guideline on how to select Artificial Magnetic Conductors (AMCs) is explained with an example of a blended checkerboard architecture where a 10-dB RCS reduction is observed over 83% of the bandwidth. Further, by modifying the architecture of the blended checkerboard metasurface, the 10-dB RCS reduction bandwidth increased to 91% fractional bandwidth. All the proposed architectures are validated using measured data for fabricated prototypes. Critical steps for designing the ultrabroadband RCS reduction checkerboard surface are summarized. Finally, a broadband technique to reduce the RCS of complex targets is presented. By using the proposed technique, the problem of reducing the RCS contribution from such multiple-bounces simplifies to identifying and implementing a set of orthogonal functions. Robust guidelines for avoiding grating lobes are provided using array theory. The 90 degree dihedral corner is used to verify the proposed technique. Measurements are reported for a fabricated prototype, where a 70% RCS-reduction bandwidth is observed. To generalize the method, a 45 degree dihedral corner, with a quadruple-bounce mechanism, is considered. Generalized guidelines are summarized and applied to reduce the RCS of complex targets using the proposed method. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

abstract: This study summarizes survey responses on perceived challenges by conductors who a) identify as female, b) are not citizens of the United States, c) are currently living in the United States, and d) are working in professional positions in the field of orchestral conducting. The goal of the survey was to query the concept of “double minority” (female and non-native to the United States) and to gain insight into the conductors’ self-perceptions and perceived challenges they encounter during their employment and career advancement in the United States. The survey covered four main areas: educational background, immigration status, the employing orchestra or organization’s budget, and conductors’ challenges and perceptions. Considering the sensitivity of the topic and following best practices of human subjects’ research, participant identities were coded with letters. Participants expressed more certainty about the issues and challenges concerning how they were perceived as females than as immigrants. There was insufficient data to correlate the budget of the orchestra with the willingness of the institution to be a visa sponsor. This study’s findings suggest that there are areas that should be further explored such as: the effect a conductor’s nationality has on their career and reception in the United States; how potential motherhood affects the conductors’ careers; organizations’ willingness and ability to hire immigrants, offer sponsorship, and assist the artist in the transition out of the student visa status; and the perceptions and experiences of being an immigrant conductor in the United States. / Dissertation/Thesis / Doctoral Dissertation Music 2020

Mott insulators are a family of materials in which strong electron-electron interactions induce an unconventional insulating state in the system that would otherwise behave as an electrical conductor according to the non-interacting band theory. In particular, the nature of the Mott metal-insulator transition (MIT) has been the subject of intense research interest because it can involve a complicated interplay between magnetic and electronic properties. In some Mott systems, Mott transitions occur in the one-step process, from an antiferromagnetic insulator (AFI) to a paramagnetic metal phase (PMM), while in other Mott systems a two-step transition with an intermediate antiferromagnetic metal (AFM) phase can be observed. Since 2015, the muon spin relaxation (𝜇SR) group at Columbia University started systematic 𝜇SR studies on a series of Mott systems, including one-step transition Mott systems 𝑅𝐸NiO₃ and V₂O₃, as well as two-step transition Mott systems Ba(Co, Ni)S₂, Ni(S, Se)₂ and (La, Sr)VO₃. This dissertation first introduces the comprehensive 𝜇SR research on multiple families of Mott systems conducted by our 𝜇SR group, including 𝑅𝐸NiO₃, V₂O₃, and BaCoS₂. Then the 𝜇SR experimental findings on the Mott system NiS₂₋ₓSeₓ will be presented, which is the most extensively studied material in this thesis. The NiS₂₋ₓSeₓ system is of particular interest because there is a large region of intermediate AFM state emerging between AFI and PMM states with Se doping, making it an ideal platform to provide information on static magnetism in the AFM state and thus can help us better understand the evolution of magnetic NiS₂₋ₓSeₓ, with our key findings being: (1) The AFM state of the NiS₂₋ₓSeₓ system shows significantly random spin correlations, and the magnetic order is suppressed by a gradual reduction of the ordered moment size, with a nearly full ordered volume fraction until very close to the AFM-PMM boundary. (2) No signature of dynamic critical behavior was observed in the thermal phase transition, indicating a first-order thermal phase transition. The next part of this dissertation presents our computational simulations on the NiS₂₋ₓSeₓ system. Dipolar field simulations have shown that only the combination of easy axis randomization and Ni moment dilution in NiS₂ can lead to the internal field distribution corresponding to the observed 𝜇SR spectrum in the AFM region. Also, this picture could qualitatively explain the neutron and muon results consistently, thus reconciling the seemingly contradicting experimental results by 𝜇SR and the previous neutron scattering studies shown in the AFM region. Furthermore, we propose a percolation model that can capture both the charge and spin connections of the interpenetrating percolating spin and charge networks in the NiS₂₋ₓSeₓsystem, which raises the possibility of "compromising metallicity and magnetic order" in the two-step Mott transition evolving AFI to AFM to PMM states in NiS₂₋ₓSeₓ.