Nickel-Yttria Stabilized Zirconia (Ni-YSZ) cermets are used as anodes in solid oxide fuel cells. These anodes are stable for tens of thousands of hours during operation and have low cost. In this work, Ni-YSZ anodes are infiltrated with nickel nanoparticles to increase the density of electrochemical reaction sites and improve their performance. However, infiltrated nickel nanoparticles are isolated from one another, so they are not electrochemically active. Two approaches have been utilized to activate infiltrated nickel nanoparticles: in-situ nickel spreading and simultaneous infiltration of nickel with Gd0.1Ce0.9O2-δ (GDC). In-situ nickel spreading, which occurs during exposure to anodic mass transfer limited currents, connects and activates nickel nanoparticles, improving anode performance but inherently causing nanoparticle coarsening. Simultaneous infiltration of Ni and GDC results in substantially improved anode performance, and the infiltrated nanostructures are more stable than infiltrated nickel. Detailed analysis of the electrochemical impedance by equivalent circuit modeling is used to separate the contributions of nickel and GDC infiltrants to the overall cell performance.

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No description available.

This project revolves around the measurement of T1 and T2 relaxation times in the ratbrain, in a multi-center way. That is to say, elaborate an efficient protocol to calculate highresolution 3D map of the brain. This protocol should be applied in different centers andreturn similar results. Finally, procedures should be defined to ease the collaborationbetween the different centers. The first step consisted in in vitro experiments, in whichdifferent sequences were tested. It resulted that the MDEFT sequence with inversionpreparation (MPRAGE) gives the best results in the shortest time for T1. For T2, theMSME sequence was chosen. The next step moved on in vivo experiments on three rats inorder to get used to manipulating living animals and make new adjustments. As thephysiology is not the same on in vitro and in vivo experiments, some parameters had to beslightly adapted. Once the final 2h-protocol was established, it was tested on a populationof ten rats. Experiments were made at the GIN and CRMBM. Different fitting pipelineswere tried (GIN, CRMBM, MIRCEN). The brain was segmented into different regions. Itresulted that the GIN and CRMBM pipelines return the same T1 values using the differentdatasets. The MIRCEN pipeline under-estimates by 200 ms. The three pipelines return similar T2 values. The GIN and CRMBM datasets provide comparable T1 values, but theGIN center presents slightly higher T2 values. Regarding the multi-center collaboration,the different pipelines were ported to the VIP platform so that the scientific community caneasily reuse them.

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Quantum mechanics has a long history of helping computer science. For a long time, it provided help only at the hardware level by giving a better understanding of the properties of matter and thus allowing the design of ever smaller and ever more efficient components. For the last few decades, much research has been dedicated to finding whether one can change computer science even more radically by using the principles of quantum mechanics at both the hardware and algorithm levels. This field of research called Quantum Information Processing (QIP) has rapidly seen interesting theoretical developments: it was in particular shown that using superposition of states leads to computers that could outperform classical ones. The experimental side of QIP however lags far behind as it requires an unprecedented amount of control and understanding of quantum systems. Much effort is spent on finding which particular systems would provide the best physical implementation of QIP concepts. Because of their nearly endless versatility and the high degree of control over their synthesis, organic materials deserve to be assessed as a possible route to quantum computers. This thesis studies the QIP potential of spin degrees of freedom in several such organic compounds. Firstly, a study on low-spin antiferromagnetic rings is presented. It is shown that in this class of molecular nanomagnets the relaxation times are much longer than previously expected and are in particular long enough for up to a few hundred quantum operations to be performed. A detailed study of the relaxation mechanisms is presented and, with it, routes to increasing the phase coherence time further by choosing the suitable temperature, isotopic and chemical substitution or solvent. A study of higher-spin systems is also presented and it is shown that the relaxation mechanisms are essentially the same as in low-spin compounds. The route to multi-qubit system is also investigated: the magnetic properties of several supermolecular assemblies, in particular dimers, are investigated. Coupling between neighbouring nanomagnets is demonstrated and experimental issues are raised concerning the study of the coherent dynamics of dimers. Finally a study of the purely organic compound phenanthrene is reported. In this molecule the magnetic moment does not result from the interactions between several transition metal ions as in molecular nanomagnets but from the photoexcitation of an otherwise diamagnetic molecule. The interest of such a system in terms of QIP is presented and relaxation times and coupling to relevant nuclei are identified.

Neste trabalho, descrevemos um espectrômetro ótico para medidas de Dicroismo Circular Magnético (DCM), utilizado nas seguintes experiências: 1) Medidas de tempo de relaxação spin-rede (T1) para centros F em NaCl, NaBr, CsBr e CsCl, a temperatura de 1,8&#176K em campos magnéticos até 17000Gs. Verificamos a validade da teoria da referência (8) para explicar as diferenças observadas, no comportamento de \'T IND.1\', para halogenetos com diferentes íons alcalinos, bem como diferentes estruturas. Comprovamos que a interação hiperfina ainda continua a ser o mecanismo mais importante para esses centros. Verificamos também que, para temperaturas entre 6&#176K e l5&#176K, os valores de experimentais para T1, em KBr, concordam razoavelmente com a teoria da referência (21). Esta terapia é uma extensão daquela da referência (8). 2) Espectros de DCM para KCl: Co++ e CaF2: Co++ foram obtidos para campos magnéticos ate 56KGs e temperaturas entre 1,8&#176K e 4,2 &#176K. Os resultados obtidos mostraram ser concordantes com a hipótese dos centros Co++ ocuparem sítios intersticiais na rede de KCl. / In this work we describe a Magnetic Circular Dicroism Spectrometer wich was used in the following experiments: 1) We measured the spin-lattice relaxation time (T1) for F centers in NaCl, NaBr, CsBr and CsCl, at 1,8&#176K in magnetic fields up to 15000Gs. We verified the suitability of the theory of ref.(O8) to explain the differences observed for halides of differents alkali ions as well as for different structures. This proves that the hyperfine interaction is the most important mechanism for this kind of centers. We also verified that, for temperatures between 6&#176K and l5&#176K, T1, the T1 experimental values fits the theory of ref.(21) reasonably well ,for F centers in KBr. This theory is an extension of that of ref.(8). 2) We obtained the MCD spectra for KCl: Co++ and CaF2: Co++ in different magnetic fields up to 56KGs, and in temperature range between 1,8 &#176K and 4,2&#176K. Our results are consistent with the assumption that Co++ centers are intersticial in KCl lattice.

Os tempos de relaxação longitudinal (T1) e transversal (T2) são largamente utilizados em medidas qualitativas e quantitativas em Ressonância Magnética Nuclear no domínio do tempo (RMN-DT). As constantes de tempo T2 e T1 são medidas com as sequências de pulsos Carr-Purcel-Meiboom-Gill (CPMG) e Inversão Recuperação (IR), respectivamente. Além dessas sequencias, também têm sido desenvolvidos outros métodos que permitem a medição de T1 e T2 em um único experimento. Dentre esses, destacam-se os provenientes da condição Continuous Wave Free Precession: CWFP e CP-CWFP (Carr-Purcel-CWFP) com ou sem alternância de fase entre os pulsos que compõe o trem de pulsos de 90º desses métodos. Baseando-se no fato de que os métodos provenientes da condição CWFP têm sido promissores para a determinação das constantes de tempo de uma forma rápida, esse trabalho visou aprofundar o estudo das sequências de pulsos oriundas dessa condição a fim de desenvolver um método de determinação rápida da constante de tempo T1 em um único experimento e também implementar a condição CWFP em sequências de pulsos 2D (2D-CWFP). Utilizando-se de pulso de baixo ângulo de rotação (θ ~10 graus) foi possível determinar a constante de tempo T1 utilizando a condição CWFP, esse método foi denominado de CWFP-T1. Contudo, este apresentou um sinal com baixa razão sinal ruído (S/R) devido aos baixos valores de q. Para minimizar esse efeito foram estudados cinco métodos de redução de ruído que podem ser aplicados em sinais de RMN-DT após a aquisição, sendo que, dentre os métodos estudados foi comprovado que os filtros wavelet (WA) e o Savistiky-Goaly (SG) são os mais eficazes para redução do ruído sem distorcer as informações da amostra. Além disso, o sinal obtido pelo método CWFP-T1 associado ao filtro WA demonstrou ser eficiente para determinação de gordura em carne bovina. Dentre os métodos 2D-CWFP desenvolvidos neste trabalho, o CPMG-CWFP-T1 apresentou vantagem em tempo de experimento sobre o método IR-CPMG. Além disso, o sinal adquirido pelo método CPMG-CWFP-T1 quando associado ao filtro SG propiciou a obtenção de mapas com melhor resolução na dimensão de T1, que as outras sequências de pulsos abordadas neste estudo, e também demonstrou ser um método promissor para a análise da carne e gordura bovina. Esta foi a primeira vez em que a constante de tempo T1 foi utilizada como dimensão de aquisição de uma forma conveniente em experimento 2D de correlação dos tempos de relaxação, visto que aquisições dessa natureza geralmente requerem longos tempos de experimento. / The longitudinal (T1) and transverse (T2) relaxation times are widely used in the qualitative and quantitative measurements in time domain Nuclear Magnetic Resonance (TD-NMR). Those relaxation times are generally measured by the Carr-Purcel-Meiboom-Gill (CPMG) and Inversion Recovery (IR) pulse sequences, respectively. In addition to these sequences, other methods have been development, which makes it possible to measure T1 and T2 in a single experiment. Among these, a special reference is made those ones coming from the Continuous Wave Free Precession condition: CWFP and CP-CWFP (Carr-Purcel-CWFP) with or without phase alternation between the pulses that make up the pulse train of 90º of these methods. Based on the fact that the methods from the CWFP condition have been promising to determine the time constants fast, the purpose of this work was to deepen the study of the sequences from that condition in order to develop a rapid method to determine the T1 relaxation time in a single experiment, and also to implement the CWFP condition in 2D sequences (2D-CWFP). Using a small flip angle (θ ~10 degrees) it was possible to determine the T1 relaxation time using the CWFP condition; this method was named CWFP-T1­. Nevertheless, this sequence has a signal with a low signal-to-noise ratio (SNR) because of the small values of q. In order to minimize this effect was studied five denoise methods to applied in the post-acquisition TD-NMR signals. Among the denoise methods studied, the wavelet (WA) and the Savistiky-Goaly (SG) are the most effective to reduce the noise of the signal without distorting the sample information. In addition, the CWFP-T1 signal associated to the WA has shown to be effective for determining the fat in beef samples. Among the 2D-CWFP methods developed in this work, the CPMG-CWFP-T1 had advantage in the experimental time compared with the IR-CPMG method. Furthermore, the signal acquired by CPMG-CWFP-T1 sequence, when associated with the SG filter, had 2D maps with the best resolution in the T1 dimension than the other sequences addressed in this work and also proved to be effective to analyze fat beef. This was the first time that T1 time constant was encoded in the acquisition dimension at a convenient way in the 2D experiments of relaxation times correlation, once such acquisitions generally require extensive experimental time.

Neste trabalho, descrevemos um espectrômetro ótico para medidas de Dicroismo Circular Magnético (DCM), utilizado nas seguintes experiências: 1) Medidas de tempo de relaxação spin-rede (T1) para centros F em NaCl, NaBr, CsBr e CsCl, a temperatura de 1,8&#176K em campos magnéticos até 17000Gs. Verificamos a validade da teoria da referência (8) para explicar as diferenças observadas, no comportamento de \'T IND.1\', para halogenetos com diferentes íons alcalinos, bem como diferentes estruturas. Comprovamos que a interação hiperfina ainda continua a ser o mecanismo mais importante para esses centros. Verificamos também que, para temperaturas entre 6&#176K e l5&#176K, os valores de experimentais para T1, em KBr, concordam razoavelmente com a teoria da referência (21). Esta terapia é uma extensão daquela da referência (8). 2) Espectros de DCM para KCl: Co++ e CaF2: Co++ foram obtidos para campos magnéticos ate 56KGs e temperaturas entre 1,8&#176K e 4,2 &#176K. Os resultados obtidos mostraram ser concordantes com a hipótese dos centros Co++ ocuparem sítios intersticiais na rede de KCl. / In this work we describe a Magnetic Circular Dicroism Spectrometer wich was used in the following experiments: 1) We measured the spin-lattice relaxation time (T1) for F centers in NaCl, NaBr, CsBr and CsCl, at 1,8&#176K in magnetic fields up to 15000Gs. We verified the suitability of the theory of ref.(O8) to explain the differences observed for halides of differents alkali ions as well as for different structures. This proves that the hyperfine interaction is the most important mechanism for this kind of centers. We also verified that, for temperatures between 6&#176K and l5&#176K, T1, the T1 experimental values fits the theory of ref.(21) reasonably well ,for F centers in KBr. This theory is an extension of that of ref.(8). 2) We obtained the MCD spectra for KCl: Co++ and CaF2: Co++ in different magnetic fields up to 56KGs, and in temperature range between 1,8 &#176K and 4,2&#176K. Our results are consistent with the assumption that Co++ centers are intersticial in KCl lattice.

Nuclear magnetic resonance (NMR) provides a convenient probe for the study of molecular reorientation in liquids because nuclear spin-lattice relaxation times are dependent upon the details of molecular motion. The combined application of Raman and Infrared (IR) lineshape analysis can furnish more complete information to characterize the anisotropic rotation of molecules. Presented here are the studies of NMR relaxation times, together with Raman/IR Mneshape analysis of the solvent and temperature dependence of rotational diffusion in 1,3,5-tribromobenzene and 1,3,5-trifluorobenzene. In these experiments, it was found that the rotational diffusion constants calculated from Perrin's stick model were two to three times smaller than the measured values of D, and D,,. Similarly, rotational diffusion constants predicted by the Hu-Zwanzig slip model were too large by a factor of 2. Application of the newer Hynes-Kapral-Weinberg model furnished rotational diffusion constants that were in reasonable agreement with the experimental results. The vibrational peak frequencies and relaxation times of the isotropic Raman spectra of the υ1 modes of CD2Br2 and CHBr3 were studied in solution. The frequency shifts in non-interactive solvents were explained well on the basis of solution variations in the dispersion energy. In Lewis bases, the displacements were in some, but not all, cases greater than predicted. On the other hand, it was found that the vibrational relaxation times of the C-H/C-D modes decreased dramatically in all Lewis base solvents. Therefore, it was concluded that relaxation times of the υ1 modes, rather than frequency shifts, furnish a more reliable measure of hydrogen bonding interactions of halomethanes in solution.