Nesta tese investigamos o estado normal (T > Tc) dos Yba2Cu3O6+x supercondutores de alto Tc. As técnicas da RMN e RQN foram empregadas para estudar as respostas estática e dinâmica do sistema de spins eletrônicos em função da temperatura, para diversas concentrações de oxigênio: x = 0.5 (cristal 1), 0.92 (cristal 2), 0.94 (cristal 3) e 1.0 (cristais 4 e 5). Focalizando diferentes sítios nucleares a RMN pode fornecer uma informação mais rica da susceptibilidade dinâmica, X (q.w), abrangendo diferentes regiões da Zona de Brillouin (ZB). Com os sítios do 17O(2,3) e do 89Y sensoreamos a região próxima ao centro do ZB, q == 0, enquanto que com o sitio do Cu(2) exploramos o extremo do ZB, (q == QAF). Foi realizado um estudo comparativo da RMN dos sítios do Cu(2), do O(2,3) e do Y sobre o cristal 1. Da comparação entre os deslocamentos hiperfinos magnéticos do Y e do O(2,3) extraímos as contribuições orbitais e as constantes de acoplamento hiperfino do Y. A razão entre as relaxações spin-rede do O(2,3) e do Y mostrou-se independente da temperatura, e próxima do esperado teoricamente a partir das constantes hiperfinas no cenário do hamiltoniano de Mila e Rice. Questões como a dependência da taxa de relaxação spin-rede (T1-1) com a intensidade do campo e a anisotropia da susceptibilidade estática de spin foram estudadas sobre o cristal 2. Acima de Tc, para o Cu(2), não foi encontrada nenhuma dependência de T1 com a intensidade do campo. Os resultados sobre o Y indicam uma anisotropia da susceptibilidade e do tensor de acoplamento hiperfino. Uma extensa comparação entre os resultados da RMN e da Difusão Inelástica de Nêutrons (DIN) foi realizada sobre as mesmas amostras (cristais 4 e 5), fato inédito ate então. Propõe-se um modelo gaussiano para X\"~q,o», compatível com as experiências de nêutrons, no qual o comprimento de correlação ~ foi fixado pelos resultados da DIN sobre o cristal 2. Analisando a relaxação spin-spin do Cu(2), 63(T2g)-1, em função deste modelo, extraímos a susceptibilidade estática X\'(q=QAF) em unidades absolutas e encontramos um fator de Stoner X\'(q=QAF) / X\'(q=O) ~ 10. Da análise conjunta de 63(T1T)-1 e 63 (T2g)-1 obtivemos a energia característica das flutuações AF, rAF::::3:0meV, em excelente acordo com a DIN. Estes mesmos resultados permitiram evidenciar, exclusivamente através do RMN, quando ocorre a abertura de um gap de spin. Neste trabalho mostramos que resultados da DIN são compatíveis com a RMN para o sitio do Cu(2), porem, sérias dificuldades são encontradas para explicar os resultados sobre os sítios do Y e, principalmente, do O(2,3). As alternativas para este problema são discutidas. Os resultados obtidos nesta tese levaram ao estabelecimento de um diagrama de fase, segundo a RMN, do estado normal dos Yba2Cu3O6+x supercondutores, cobrindo do regime sub-dopado ao regime sobre-dopado, passando pela composição de dopagem ótima. / The normal state(T > Tc) of the high Te superconducting Yba2Cu3O6+x was studied. The NMR and NQR techniques were employed in order to investigate the static and dynamic responses of the electronic spin system as function of temperature, for the following oxygen contents: x = 0.5 (crystal 1), 0.92 (crystal 2), 0.94 (crystal 3) e 1.0 (crystals 4 and 5). Focusing various nuclear sites the NMR could give a more rich information of the dynamical susceptibility, X(q,ffi), probing different regions of the Brillouin Zone (ZB). With 17O(2,3) and 89Y sites the BZ center, q:: 0, was studied, while with the Cu(2) site it was the BZ extreme, (q:: QAF) that was investigated. In crystal 1 we have compared the NMR of the Cu(2), O(2,3) and Y sites. From the comparison between the Y and O(2,3) magnetic hyperfine shift we have extracted the orbital contributions and the Y hyperfine coupling tensor. The ratio between the O(2,3) and Y nuclear spin lattice relaxation rate was found to be temperature independent, and its value was in fair agreement with what it was expected theoretically from the coupling constants within the picture of the Mila-Rice Hamiltonian. Problems such as the field intensity dependence of the spin-lattice -relaxation rate (T1-1) and the anisotropy of the static susceptibility where investigated in crystal 2. Above Tc, for the Cu(2) site, we have not found any field dependence of T1. Our results on the Y site indicate an anisotropy of both the static susceptibility and the Y coupling tensor. An extensive comparison between the NMR and the Inelastic Neutron Diffusion (IND) results was done in the very same samples, crystals 2 and 4. In accordance to neutron data a Gaussian model for X\"AF( q,ro) is proposed, in which the coherence length ~ was fixed by the IND results in crystal 2. Analyzing the Cu(2) nuclear spin-spin relaxation rate, 63(T2g)-1, as function of this model, we have extracted the staggered susceptibility X\'(q=QAF) in absolute units, finding a Stoner factor X \'( q=QAF) / X\'( q=O) ~ 10. From the analysis of 63(T1T)-1 together with 63(T2g)-1 we have obtained the AF characteristic energy, rAF ::::l 30meV, in excellent agreement with IND. These results provided us a powerful method to evidence the opening of a spin pseudo gap, exclusively from the NMR results. A consistent picture arise from the comparison between IND and the Cu(2) NMR. In contrast, it is hard to explain the Y and, specially, the O(2,3) results within this same picture. The theoretical alternatives to this puzzle are discussed. The whole set of results we have obtained led us to propose a NMR based phenomenological phase diagram for the normal state of the superconducting Yba2Cu3O6+x, covering from the under doped regime to the over doped regime, passing through the optimal doping.

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The thesis deals with RF spectroscopic methods, which are applicable for the detection of hazardous substances such as explosives or drugs. Particular attention is focused on promising method of nuclear quadrupole resonance. Abroad this method has recently been applied in the detection of energetic materials in hazardous locations. The cornerstone of the nuclear quadrupole resonance is to evaluate the interaction between electromagnetic radiation, in the range of medium to very short waves, and the researched substance. Observed parameter are the resonant frequencies of the substance. Spectral analysis of signal is used for their evaluation. Resonant frequencies are always typical for the crystalline structure, therefore every explosive or drug is clearly identifiable by this method.

Land mines are a major humanitarian problem with millions of active mines in place around the world. Since these mines can have little metal in them, novel detection techniques are needed. Nuclear Quadrupole Resonance (NQR) is one such technique. Unfortunately, NQR is highly succeptible to radio frequency interference (RFI). A significant contribution of this thesis is the development of a custom, experimental data acquisition system designed and built specifically for capturing RFI at frequencies significant to NQR land mine detection systems. Another major contribution is the development of data analysis techniques for determining the number of reference antennas required to effectively cancel out RFI at frequencies and in environments typical of an NQR land mine detection system.

La conservation des informations dans les industries dont le processus de transformation est divergent à toujours posé d'important contraintes, et l'industrie du bois n'y manque pas. Les solutions de traçabilité existantes à l'heure actuelle ne permettent pas de conserver ces informations tout au long du cycle de vie du produit bois. L'objectif de cette thèse est de montrer la faisabilité de deux concepts permettant d'améliorer la conservation de l'information : le paradigme de matière communicante et le paradigme de Virtual Manufacturing. Avec le premier paradigme, il est possible de conserver les informations relatives à l'origine du produit grâce à un marquage chimique introduit dans l'ensemble de la matière que nous identifions par Résonance Quadrupolaire Nucléaire. Dans le deuxième paradigme pour anticipons les caractéristiques biométriques des produits finaux en numérisant la matière et en virtualisant les opérations de transformation. Grâce à cela, il est possible de déterminer, malgré l'imperfection des données et des décisions les caractéristiques des produits / Information conservation in the divergent process has always imposed important constraints. In the Wood industry, in which the problem is present, has no solution to conserve information all along the wood life cycle. This thesis goal is to validate the use of two new paradigms allowing improving the information conservation: the communicating material and the virtual manufacturing. With the first one, the wood material is intrinsically marked with chemical product which can be identify with the Nuclear Quadrupole Resonance and allow conserving the material origin. With the second one, it is possible to anticipate sawmill production by foresee the final product characteristics

The thesis deals with the NQR spectroscopy, which is one of the modern non-destructive measurement and diagnostic methods for the characterization of various materials. It is using a quadrupole moment - a property of atomic nuclei of certain isotopes. A method of nuclear quadrupole resonance (NQR) is in principle very similar to nuclear magnetic resonance (NMR). Thesis in the theoretical part analyse the principles of NMR and NQR, describes the possible use of this method to detect for example explosives, drugs, and other chemicals. In the following chapters are analysed the key parameters of NQR spectrometer and the principle of the chosen measurement method. The practical part deals with the individual components of NQR spectrometer, the design of possible improvements and programming of the measuring sequence. In the final chapter are processed the measurements of the submitted samples.

Nuclear quadropole spectroscopy is a modern analytical method for detecting specific solid state materials, e.g. explosives, drugs etc. It uses phenomenon of atomic nucleus called nuclear quadrupole moment. NQR method is very similar to common nuclear magnetic resonance (NMR) that is why major principles are explained using NMR. The thesis deals with basic principle of NQR, its usage for explosives detection and also detection of other chemical compounds and many other useful applications. The thesis deals with specific circuit design, techniques for sufficient sensitivity, impedance matching and circuit isolation. Practical part consists of simulations as well as designs of a few impedance transformers, pi-networks, and coils. Also experimental probe was created. In the last part, NQR workplace was assembled and a few chemical compounds were detected. These were KClO3, NaClO3 and NaNO2 . Finally minimum detectable amount of potassium chlorate as the strongest signal of these was determined.

This thesis addresses a number of problems all related to parameter estimation in sensor array processing. The unifying theme is that some of these parameters are known before the measurements are acquired. We thus study how to improve the estimation of the unknown parameters by incorporating the knowledge of the known parameters; exploiting this knowledge successfully has the potential to dramatically improve the accuracy of the estimates. For covariance matrix estimation, we exploit that the true covariance matrix is Kronecker and Toeplitz structured. We then devise a method to ascertain that the estimates possess this structure. Additionally, we can show that our proposed estimator has better performance than the state-of-art when the number of samples is low, and that it is also efficient in the sense that the estimates have Cram\'er-Rao lower Bound (CRB) equivalent variance. In the direction of arrival (DOA) scenario, there are different types of prior information; first, we study the case when the location of some of the emitters in the scene is known. We then turn to cases with additional prior information, i.e.~when it is known that some (or all) of the source signals are uncorrelated. As it turns out, knowledge of some DOA combined with this latter form of prior knowledge is especially beneficial, giving estimators that are dramatically more accurate than the state-of-art. We also derive the corresponding CRBs, and show that under quite mild assumptions, the estimators are efficient. Finally, we also investigate the frequency estimation scenario, where the data is a one-dimensional temporal sequence which we model as a spatial multi-sensor response. The line-frequency estimation problem is studied when some of the frequencies are known; through experimental data we show that our approach can be beneficial. The second frequency estimation paper explores the analysis of pulse spin-locking data sequences, which are encountered in nuclear resonance experiments. By introducing a novel modeling technique for such data, we develop a method for estimating the interesting parameters of the model. The technique is significantly faster than previously available methods, and provides accurate estimation results. / Denna doktorsavhandling behandlar parameterestimeringsproblem inom flerkanals-signalbehandling. Den gemensamma förutsättningen för dessa problem är att det finns information om de sökta parametrarna redan innan data analyseras; tanken är att på ett så finurligt sätt som möjligt använda denna kunskap för att förbättra skattningarna av de okända parametrarna. I en uppsats studeras kovariansmatrisskattning när det är känt att den sanna kovariansmatrisen har Kronecker- och Toeplitz-struktur. Baserat på denna kunskap utvecklar vi en metod som säkerställer att även skattningarna har denna struktur, och vi kan visa att den föreslagna skattaren har bättre prestanda än existerande metoder. Vi kan också visa att skattarens varians når Cram\'er-Rao-gränsen (CRB). Vi studerar vidare olika sorters förhandskunskap i riktningsbestämningsscenariot: först i det fall då riktningarna till ett antal av sändarna är kända. Sedan undersöker vi fallet då vi även vet något om kovariansen mellan de mottagna signalerna, nämligen att vissa (eller alla) signaler är okorrelerade. Det visar sig att just kombinationen av förkunskap om både korrelation och riktning är speciellt betydelsefull, och genom att utnyttja denna kunskap på rätt sätt kan vi skapa skattare som är mycket noggrannare än tidigare möjligt. Vi härleder även CRB för fall med denna förhandskunskap, och vi kan visa att de föreslagna skattarna är effektiva. Slutligen behandlar vi även frekvensskattning. I detta problem är data en en-dimensionell temporal sekvens som vi modellerar som en spatiell fler-kanalssignal. Fördelen med denna modelleringsstrategi är att vi kan använda liknande metoder i estimatorerna som vid sensor-signalbehandlingsproblemen. Vi utnyttjar återigen förhandskunskap om källsignalerna: i ett av bidragen är antagandet att vissa frekvenser är kända, och vi modifierar en existerande metod för att ta hänsyn till denna kunskap. Genom att tillämpa den föreslagna metoden på experimentell data visar vi metodens användbarhet. Det andra bidraget inom detta område studerar data som erhålls från exempelvis experiment inom kärnmagnetisk resonans. Vi introducerar en ny modelleringsmetod för sådan data och utvecklar en algoritm för att skatta de önskade parametrarna i denna modell. Vår algoritm är betydligt snabbare än existerande metoder, och skattningarna är tillräckligt noggranna för typiska tillämpningar. / <p>QC 20131115</p>

Spectroscopic techniques allow for studies of materials and organisms on the atomic and molecular level. Examples of such techniques are nuclear magnetic resonance (NMR) spectroscopy—one of the principal techniques to obtain physical, chemical, electronic and structural information about molecules—and magnetic resonance imaging (MRI)—an important medical imaging technique for, e.g., visualization of the internal structure of the human body. The less well-known spectroscopic technique of nuclear quadrupole resonance (NQR) is related to NMR and MRI but with the difference that no external magnetic field is needed. NQR has found applications in, e.g., detection of explosives and narcotics. The first part of this thesis is focused on detection and identification of solid and liquid explosives using both NQR and NMR data. Methods allowing for uncertainties in the assumed signal amplitudes are proposed, as well as methods for estimation of model parameters that allow for non-uniform sampling of the data. The second part treats two medical applications. Firstly, new, fast methods for parameter estimation in MRI data are presented. MRI can be used for, e.g., the diagnosis of anomalies in the skin or in the brain. The presented methods allow for a significant decrease in computational complexity without loss in performance. Secondly, the estimation of blood flow velo-city using medical ultrasound scanners is addressed. Information about anomalies in the blood flow dynamics is an important tool for the diagnosis of, for example, stenosis and atherosclerosis. The presented methods make no assumption on the sampling schemes, allowing for duplex mode transmissions where B-mode images are interleaved with the Doppler emissions.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23733号 / 理博第4823号 / 新制||理||1690(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 竹腰 清乃理, 准教授 武田 和行, 教授 吉村 一良 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM