京都大学 / 新制・課程博士 / 博士(工学) / 甲第25014号 / 工博第5191号 / 新制||工||1991(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 佐藤 徹, 教授 田中 庸裕, 教授 佐藤 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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A teoria de campo médio para o modelo de Ashkin-Teller com interações ferromagnéticas de longo alcance na presença de campos magnéticos aleatórios foi desenvolvida. Isso foi conseguido através do uso do truque de réplicas para a obtenção da energia livre e do estudo analítico das equações integrais acopladas dos parâmetros de ordem, da estabilidade de suas soluções e das suas expansões para T &#8804 Tc. Inicialmente, foram determinadas as expressões gerais das funções termodinâmicas do modelo no caso em que existiam três campos magnéticos aleatórios com distribuições gaussianas. Em seguida, foi examinado o caso particular do modelo com um só campo magnético aleatório na direção de Z = &#8249 &#948 S &#8250. A estratégia adotada se mostrou poderosa pois possibilitou a caracterização detalhada do diagrama de fases com várias superfícies de coexistência e das linhas de pontos críticos. As equações integrais das funções termodinâmicas desse caso particular foram discutidas e resolvidas numericamente para valores especiais das constantes de interação e da variância. Para o caso particular do modelo na presença de campos magnéticos aleatórios nas direções &#8249 S &#8250 e &#8249 &#948 &#8250, foram determinadas e discutidas as expressões das funções termodinâmicas. Foram também obtidas as equações das superfícies de instabilidade da solução paramagnética. Foi provado que a transição entre as fases paramagnética e de Baxter é sempre de primeira ordem. Outro resultado original da tese foi a verificação da existência da simetria de dilatação e contração do modelo de Potts na presença de campos magnéticos aleatórios. Essa simetria permite que o estudo da energia livre no intervalo q&#8712 (1,2) forneça o comportamento termodinâmico do sistema para todo q>2. / The meanfield theory of the long range Ashkin-Teller model in random fields was developed. This was obtained by using the replica trick and the study of the coupled integral equations for the order parameters, the stability of their solutions, and their expansions for T &#8804 Tc. Inicially, the expressions of the thermodynamic functions for the model in three random fields with Gaussian distributiuons were determined. After this, it was examined the particular case of the model with only one random field in the Z = &#8249 &#948 S &#8250 direction. The strategy revealed itself powerful by the detailed characterization of the phase diagram with several coexistence surfaces and lines of critical points. The integral equations of the thermodynamic functions for this particular case were discussed and numerically solved for special values of the interaction constants and field distribution variance. For the particular case of the model with random fields in the &#8249 S &#8250 and &#8249 &#948 &#8250, directions, the expressions were also determined and discussed. The equations of the instability surfaces for the paramagnetic solution were obtained, and it was proved that the para-Baxter transition line is always of first order. Another original result of the thesis was the verification of the the existence of the dilatation and contration symmetry in the Potts model with random fields. This symmetry permits that the study of the free energy in the q&#8712(1,2) interval supplies the thermodynamics behavior of the system for q>2.

Made available in DSpace on 2014-12-17T15:14:51Z (GMT). No. of bitstreams: 1 RobertoTGO_DISSERT.pdf: 394069 bytes, checksum: fbb8faf7e24cc92335302e442b92ec43 (MD5) Previous issue date: 2010-02-22 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / In this work we study the phase transitions of the ferromagnetic three-color Ashkin-Teller Model in the hierarquical lattice generated by the Wheatstone bridge using real space renormalization group approach. With such technique we obtain the phase diagram and its critical points with respective critical exponents v. This model presents four phases: ferromagnetic, paramagnetic and two intermediates. Nine critical points were found, three of which are of Ising model type, three are of four states Potts model type, one is of eight states Potts model type and the last two which do not correspond to any Potts model with integer number of states. iv / Neste trabalho estudamos as transi??es de fase do modelo de Ashkin-Teller de tr?s cores ferromagn?tico na rede hier?rquica ponte de Wheatstone utilizando o m?todo de grupo de renormaliza??o no espa?o real. Com a utiliza??o desta t?cnica obtemos o diagrama de fases e seus pontos cr?ıticos com respectivos expoentes cr?ticos v. O modelo apresenta quatro fases: ferromagn?tica, paramagn?tica e duas intermedi?rias. Nove pontos cr?ıticos foram encontrados, sendo tr?s de classe de universalidade Ising, tr?s Potts de quatro estados, um Potts de oito estados e dois com classe de universalidade n?o correspondente a nenhum Potts com n?mero inteiro de estados

A teoria de campo médio para o modelo de Ashkin-Teller com interações ferromagnéticas de longo alcance na presença de campos magnéticos aleatórios foi desenvolvida. Isso foi conseguido através do uso do truque de réplicas para a obtenção da energia livre e do estudo analítico das equações integrais acopladas dos parâmetros de ordem, da estabilidade de suas soluções e das suas expansões para T &#8804 Tc. Inicialmente, foram determinadas as expressões gerais das funções termodinâmicas do modelo no caso em que existiam três campos magnéticos aleatórios com distribuições gaussianas. Em seguida, foi examinado o caso particular do modelo com um só campo magnético aleatório na direção de Z = &#8249 &#948 S &#8250. A estratégia adotada se mostrou poderosa pois possibilitou a caracterização detalhada do diagrama de fases com várias superfícies de coexistência e das linhas de pontos críticos. As equações integrais das funções termodinâmicas desse caso particular foram discutidas e resolvidas numericamente para valores especiais das constantes de interação e da variância. Para o caso particular do modelo na presença de campos magnéticos aleatórios nas direções &#8249 S &#8250 e &#8249 &#948 &#8250, foram determinadas e discutidas as expressões das funções termodinâmicas. Foram também obtidas as equações das superfícies de instabilidade da solução paramagnética. Foi provado que a transição entre as fases paramagnética e de Baxter é sempre de primeira ordem. Outro resultado original da tese foi a verificação da existência da simetria de dilatação e contração do modelo de Potts na presença de campos magnéticos aleatórios. Essa simetria permite que o estudo da energia livre no intervalo q&#8712 (1,2) forneça o comportamento termodinâmico do sistema para todo q>2. / The meanfield theory of the long range Ashkin-Teller model in random fields was developed. This was obtained by using the replica trick and the study of the coupled integral equations for the order parameters, the stability of their solutions, and their expansions for T &#8804 Tc. Inicially, the expressions of the thermodynamic functions for the model in three random fields with Gaussian distributiuons were determined. After this, it was examined the particular case of the model with only one random field in the Z = &#8249 &#948 S &#8250 direction. The strategy revealed itself powerful by the detailed characterization of the phase diagram with several coexistence surfaces and lines of critical points. The integral equations of the thermodynamic functions for this particular case were discussed and numerically solved for special values of the interaction constants and field distribution variance. For the particular case of the model with random fields in the &#8249 S &#8250 and &#8249 &#948 &#8250, directions, the expressions were also determined and discussed. The equations of the instability surfaces for the paramagnetic solution were obtained, and it was proved that the para-Baxter transition line is always of first order. Another original result of the thesis was the verification of the the existence of the dilatation and contration symmetry in the Potts model with random fields. This symmetry permits that the study of the free energy in the q&#8712(1,2) interval supplies the thermodynamics behavior of the system for q>2.

Les lichens sont des organismes symbiotiques constitués d'un champignon (mycobionte) associé à une algue et/ou une cyanobactérie (photobionte). Leurs métabolites secondaires sont des molécules originales appartenant au groupe des depsides, depsidones, dibenzofuranes et présentent un intérêt pour la cosmétique et/ou la pharmaceutique en raison de leur propriété antibiotique, anti-inflammatoire, antioxydant, filtre UV. Nous avons choisi d'étudier le lichen Pseudevenia furfuracea qui est l'un des lichens utilisés en tant que matière première pour la parfumerie et la cosmétique (1900 tonnes / an), car il est d'une part abondant dans la nature et d'autre part, il possède des métabolites secondaires très variés. Classiquement, les extraits utilisés sont obtenus par extraction au reflux de solvants organiques; cette méthode à l'inconvénient d'induire des durées d'extractions relativement longues et est consommatrice en solvants. L'objectif de notre travail est d'extraire les métabolites secondaires d'une manière sélective et innovante tout en diminuant la durée d'extraction. Pour cela, nos travaux reposent sur l'extraction assistée sous micro-onde (EAM) combinée ou non aux liquides ioniques. Dans ce dessein, deux familles de liquides ioniques (LIs) "hydrophiles" et "hydrophobes" ayant un cation imidazolium et pyridinium ont été synthétisés. Trois différentes préparations de lichen (mixé, broyé au mortier et broyé planétaire) ont été effectuées en faisant varier la granulométrie et chaque préparation a été étudiée par microscopie électronique à balayage. L'optimisation de l'EAM a été effectuée à une température d'extraction optimale de 75 °C et a permis de générer un énorme gain de temps (24 h sous conditions classiques contre 15 min sous irradiation micro-onde). Une étude comparative des taux d'extraction entre l'EAM et l'extraction en condition classique a été éffectuée par analyse au spectrodensitomètre CAMAG®, celle-ci a montré que la première est plus performante dans la plupart des cas. L'utilisation des liquides ioniques a mis en évidence l'existence d'une sélectivité d'extraction en fonction de la structure des LIs qui résulte d'interactions intermoléculaires entre les LIs et les substances extraites. L'effet de chaque liquide ionique sur la dégradation d'un des métabolites, en particulier l'atranorine, a également été étudié. Également, les interactions entre un liquide ionique et la surface du lichen ont été étudiées par mesure d'angle de contact et par les mesures de Brunauer Emett et Teller. Une extraction à plus grande échelle a été réalisée pour étudier la reproductibilité de la méthode et la possibilité de recycler le liquide ionique. / Lichens are symbiotic organisms constituted of fungus (mycobiont) associated to algae and/or cyanobacteria (photobiont). Their secondary metabolites are original molecules belonging to the group of depsides, depsidones, dibenzofurans. Lichens presented special interest for cosmetic and pharmaceutical industry due to their antibiotic, anti-inflammatory, antioxidant and UV filter properties. In this work we focused our study on Pseudevenia furfuracea lichen, which is intensively used as a raw material in perfumery and cosmetics (1900 tons/year), due to its large availability in nature as well as possessing various secondary metabolites. In this work we presented extraction of the secondary metabolites using a selective and innovative solventfree method in shorter extraction time in comparison to the conventional extraction methods requiring under reflux of large quantities of solvents with longer times for extraction. The proposed method is based on the use of microwave irradiation for extraction (MIE) associated to (or not) appropriate ionic liquids. Two kinds of hydrophilic or hydrophobic imidazolium- and pyridinium-based ionic liquids (ILs) were synthesized. Three different methods of grinding for lichen were used, leading to different particle size and the crushed products were observed by scanning electron microscopy (SEM). Heating optimization of MIE was performed during 15 min at optimal temperature (75 °C) (instead of 24 h under conventional heating). A comparative study of extraction rates between MIE and extraction with conventional heating was realized with a CAMAG® spectrodensitometer and results of analysis showed that MIE is efficient in most of the studied cases. The use of ionic liquids showed selectivity for extraction and it depended on the structure of ILs and also intermolecular interactions between ILs and extracted substances.Effect of each ionic liquid on the degradation of one of the secondary metabolites, atranorin, was also been studied. In addition, interactions between IL and the surface of the lichen surface were studied by measurements of the angle of contact and by Brunauer Emett and Teller measurements. Scale-up for extraction was carried out to investigate the reproducibility of the method and the possibility of reuse of the ionic liquid.

Metal acetylacetonates of the general formula [M(acac)3] (MIII=Cr, Mn, Fe, Co) are among the best investigated coordination compounds. Many of these first-row transition metal complexes are known to have unique electronic properties. Independently, photophysical research with different β-diketonate ligands pointed towards the possibility of a special effect of the 2,4,6-trimethylphenyl substituted acetylacetonate (mesacac) on the electron distribution between ligand and metal (MLCT). We therefore synthesized and fully characterized the previously unknown octahedral title complex. Its solid-state structure shows a Jahn-Teller elongation with two Mn−O bonds of 2.12/2.15 Å and four Mn−O bonds of 1.93 Å. Thermogravimetric data show a thermal stability up to 270 °C. High-resolution mass spectroscopy helped to identify the decomposition pathways. The electronic state and spin configuration of manganese were characterized with a focus on its magnetic properties by measurement of the magnetic susceptibility and triple-zeta density functional theory (DFT) calculations. The high-spin state of manganese was confirmed by the determination of an effective magnetic moment of 4.85 μB for the manganese center.

Anhand von theoretischen Untersuchungen wird eine umfassende Beschreibung von kleinen Metalloxidclustern gegeben. Bei den untersuchten Systemen handelt es sich um Aluminium- und Eisenoxid-Ionen sowie entsprechende Oxid-Cluster, die beide Metalle enthalten. Neben der Bestimmung der geometrischen Struktur der Cluster werden auch die allgemeinen elektronischen Eigenschaften der eisenhaltigen Verbindungen untersucht. Alle Vorhersagen werden durch Vergleich mit verfügbaren experimentellen Ergebnissen -- hauptsächlich aus der Infrarot-Photodissoziations- und der Photoelektronenspektroskopie -- überprüft und bewertet. Soweit möglich werden die Bewegungen von Atomen oder kleinen Gruppen innerhalb der Cluster einzelnen experimentellen Signalen zugeordnet. Besondere Aufmerksamkeit wird dem Eisendioxidmolekül und seinem Anion gewidmet. Es wird mit spezialisierten Wellenfunktionsmethoden untersucht, mit denen ab initio Franck-Condon-Simulationen einschließlich nicht-adiabatischer und Spin-Orbit-Kopplungen für die Photoionisation des Anions erstellt werden. Sie liefern Erklärungen für die komplizierte Schwingungsstruktur des experimentellen hochauflösenden Photoelektronenspektrums. / By means of theoretical investigations, a comprehensive description of small metal oxide clusters is given. The studied systems are aluminum and iron oxide ions as well as respective bi-metallic oxide clusters. Besides the determination of the geometrical structure of the clusters, the general electronic properties of the iron-containing compounds are investigated. All predictions are checked and assessed by comparison with available experimental results, mainly infrared photodissociation and photoelectron spectroscopy measurements. As far as possible, motions of atoms or small groups within the clusters are assigned to distinct experimental vibrational features. Particular attention is paid to the iron dioxide molecule and its anion. It is studied with sophisticated wave function methods based on which ab initio Franck-Condon simulations for the photodetachment from the anion, including non-adiabatic and spin-orbit couplings, are generated. They provide explanations for the complicated vibrational structure of the experimental high-resolution photoelectron spectrum.

Lithium-ion (Li-Ion) batteries are widely used in various applications and are viable for automotive applications. The effective management of Li-Ion batteries in battery electric vehicles (BEV) plays a crucial role in performance and range. One can achieve good performance and range by using efficient battery models in battery management systems (BMS). Hence, these battery models play an essential part in the development process of battery electric vehicles. Physics-based battery models are used for design purposes, control, or to predict battery behaviour, and these require much information about materials and reaction and mass transport properties. Model parameterization, i.e., obtaining model parameters from different experimental sets (by fitting the model to experimental data sets), can be challenging depending on model complexity and the type and quality of experimental data. Based on the idea of parameter sensitivity, certain current/voltage data sets could be chosen that theoretically has a more considerable sensitivity for a given model parameter that is of interest to extract. In this thesis work, different methods for extracting model parameters for a Nickel-Manganese-Cobalt (NMC) battery composite electrode are experimentally tested and compared. Specifically, model parameterization using \emph{optimal experiments} based on performed parameter sensitivity analysis has been benchmarked against a 1C discharge test and low rate pulse tests. The different parameter sets obtained have then been validated on a drive cycle and 2C pulse tests. Comparing the methods show some promising results for the optimal experiment design (OED) method, but consideration regarding the state of charge (SOC) dependencies, the number of parameters has to be further evaluated. / Litiumjonbatterier (Li-jon) används i olika applikationer och är ett bra alternativ förfordonsapplikationer. Den effektiva hanteringen av litiumjonbatterier i elbilar har en viktigroll för fordonens prestanda och räckvidd. Man kan nå bra prestanda och räckviddgenom att använda bra batterimodeller i batteriets övervakningssystem (BMS). Därförspelar dessa batterimodeller en viktig roll i utvecklingen av elbilar. Fysikbaseradebatterimodeller används för design, reglering eller för att prediktera beteendet hos batteriet,vilket kräver mycket information om material samt dess reaktion och andra beskaffenheter.Modellparametrisering, dvs. att införskaffa modellparametrar från olika experiment (genom attanpassa modell till experimentella data) kan vara utmanande beroende på modellkomplexitetoch typen samt kvalitén på experimentell data. Baserat på idén om parametersensitivitet kan data om ström och spänning väljas så att de teoretiskt har mer sensitivitet för engiven modellparameter som är av intresse att extrahera. I detta examensarbete testas ochjämförs olika metoder för att extrahera modellparametrar för en Nickelmangankobolt (NMC)batterielektrod. Mer specifikt, modellparametrisering genom optimala experiment baseradepå genomförd parametersesitivitetsanalys jämförts med 1C urladdningstest och låg nivåpulstest. Jämförande av metoderna visar goda resultat för OED metoden men flera parametrarmåste fortsatt utvärderas gällande laddningstatusberoenden (SOC).

Low-temperature magnetic force microscopy was used to study the phase diagram of a La1/3Pr1/3Ca1/3MnO3 thin film grown on a (110) NdGaO3 (NGO) substrate by pulsed laser deposition. Traditionally, one can observe the phase change at the nanoscale level as the sample is cooled from room temperature through the transition temperature to liquid nitrogen temperatures, but in this case a fixed voltage ranging from 0 V to 31 V was applied before each cooling cycle. From in and ex situ transport measurements, it is observed that the temperature of the peak of the transition increases with applied field; however, the MFM images show that the magnetic transition begins at a lower temperature with the same increase in field. Thus, this dissertation shows that a new voltage control exists for the phase transition in certain manganites. / text