京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22451号 / 工博第4712号 / 新制||工||1736(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 田中 勝久, 教授 田中 功, 教授 陰山 洋 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The research presented in this thesis is a collection of many different, yet connected, parts that stemmed from the development of a new alternative material intended to be utilised as anode material in solid oxide fuel cells. The main part is the research conducted in the development and characterisation of the novel A-site deficient La₀.2₂Sr₀.₇₋ₓCaₓTiO₃. Calcium introduction resulted in reducing this perovskite unit cell volume which, at the beginning, enhanced its electrical conductivity in reducing conditions. However, the ideal cubic symmetry coud not be maintained, as in the starting material LA₀.₂Sr₀.₇TiO₃, as a result of the increased A-site ionic radius mismatch and two lower symmetries were observed at room temperature. These were the tetragonal I4/mcm for 0.1 ≤ x ≤ 0.35 and orthorhombic Pbnm for 0.4 ≤ x ≤ 0.7. Higher temperature NPD data showed that the orthorhombic samples transformed into higher symmetries with Pbnm → I4/mcm → Pm3-m phase transitions. Detailed crystallographic analysis is discussed; where the different unit cells showed changes to the tilts of the BO₆ octahedra, along with distortions to these octahedra. DC conductivity measurements showed a high electrical conductivity of 27.5 S/cm for a pre-reduced composition La₀.₂Sr₀.₂₅Ca₀.₄₅TiO₃ at 900°C and pO₂ = 10⁻¹⁹ atm. This material showed very encouraging features; which makes it a very promising anode material for SOFCs. A study was also done which explores the best renewable energy options for the United Arab Emirates given its local climate and other aspects. The reliance on seawater desalination is argued to by unsustainable for different reasons. Thus, water security should be a main element in the planning process for adopting renewable energy technologies. A system that combines different technologies; with a focus on fuel cells technology; is outlined which is thought of to be a very promising basis for a broader system that will secure power and water in a very environment friendly way. Different compositions of the system La₀.₂Sr₀.₇₋ₓCaₓTiO₃ were also studied using AC impedance spectroscopy in order to establish whether or not this system can show a ferroelectric behaviour. Results showed a variation in the dielectric constant of different samples with temperature; however, no Curie point was observed. Nonetheless, the results did show that the different compositions were very homogeneous when fully oxygenated and there were some indications of possible symmetry changes at sub-ambient temperatures. The final part of this thesis outlined the work done towards the development of a new analytical instrument. An existing TGA instrument was altered in order to provide a simultaneous thermogravimetric analysis and DC conductivity measurement for solid solutions at controlled temperature and oxygen partial pressure. Results were obtained for different samples of the system La₀.₂Sr₀.₇₋ₓCaₓTiO₃ which showed a great dependence of the electrical conductivity on the oxygen stoichiometry in these oxides. Also, a direct method is possible with this instrument to estimate the oxygen chemical diffusion coefficient using the electrical conductivity relaxation method. This new setup will be very useful for different electrochemical and thermal studies which can broaden the understanding of the different mechanisms that affect the performance of different solid state materials.

Failure criteria play a vital role in the numerical analysis of reinforced concrete structures. The current failure criteria can be classified into two types, namely the empirical and theoretical failure criteria. Empirical failure criteria normally lack reasonable theoretical backgrounds, while theoretical ones either involve too many parameters or ignore the effects of intermediate principal stress on the concrete strength. Based on the octahedral shear stress model and the concrete tensile strength under the state of triaxial and uniaxial stress, a new failure criterion, that is, the simplified unified strength theory (UST), is developed by simplifiing the five-parameter UST for the analysis of reinforced concrete structures. According to the simplified UST failure criterion, the concrete strength is influenced by the maximum and intermediate principal shear stresses together with the corresponding normal stresses. Moreover, the effect of hydrostatic pressure on the concrete strength is also taken into account. The failure criterion involves three concrete strengths, namely the uniaxial tensile and compressive strengths and the equal biaxial compressive strength. In the numerical analysis, a degenerated shell element with the layered approach is adopted for the simulation of concrete structures. In the layered approach, concrete is divided into several layers over the thickness of the elements and reinforcing steel is smeared into the corresponding number of layers of equivalent thickness. In each concrete layer, three-dimensional stresses are calculated at the integration points. For the material modelling, concrete is treated as isotropic material until cracking occurs. Cracked concrete is treated as an orthotropic material incorporating tension stiffening and the reduction of cracked shear stiffness. Meanwhile, the smeared craclc model is employed. The bending reinforcements and the stirrups are simulated using a trilinear material model. To verify the correctness of the simplified UST failure criterion, comparisons are made with concrete triaxial empirical results as well as with the Kupfer and the Ottosen failure criteria. Finally, the proposed failure criterion is used for the flexural analysis of simply supported reinforced concrete beams. Also conducted are the punching shear analyses of single- and multi-column-slab connections and of half-scale flat plate models. In view of its accuracy and capabilities, the simplified UST failure criterion may be used to analyse beam- and slab-type reinforced concrete structures.

The site of initial metal-carbonyl bond-breaking during ligand-exchange reactions in a series of octahedral metal carbonyls of the type (L2)M(CO)4 (M = Cr, Mo, W; L2 = diphos, phen, dipy) has been determined employing infrared spectroscopy and Fourier transform nuclear magnetic resonance spectroscopy. The results of this study reveal, for all metal carbonyl complexes of the type mentioned above, that loss of CO occurs exclusively at an axial position (cis to the bidentate ligand, I^)• The dynamic nature of the five-coordinate intermediates, such as (diphos)Mo(CO)3, (phen)M(CO)3 (M = Cr, Mo, W), and (dipy)Cr(CO)3, which are generated in solution upon CO dissociation, is reported and discussed. The results of this investigation confirm that these intermediates are fluxional on the time scale of CO-exchange process. A mechanism which describes the site of initial metal-carbonyl bond-breaking and the fluxionality of the five-coordinate intermediate during ligand-exchange reactions in the complexes (L2)M(CO)4 is proposed. A kinetic study of reactions of W(CO)6 with pseudo-halide anions (NCS-, NCO-, CN-) has been initiated. The results indicate that these reactions proceed via a bimolecular path, which involves initial attack of the pseudo-halide anion at a carbonyl carbon of W(CO)6,

Le théorème de Carathéodory coloré, prouvé en 1982 par Bárány, énonce le résultat suivant. Etant donnés d Å1 ensembles de points S1,SdÅ1 dans Rd , si chaque Si contient 0 dans son enveloppe convexe, alors il existe un sous-ensemble arc-en-ciel T µ SdÅ1 iÆ1 Si contenant 0 dans son enveloppe convexe, i.e. un sous-ensemble T tel que jT \Si j • 1 pour tout i et tel que 0 2 conv(T ). Ce théorème a donné naissance à de nombreuses questions, certaines algorithmiques et d’autres plus combinatoires. Dans ce manuscrit, nous nous intéressons à ces deux aspects. En 1997, Bárány et Onn ont défini la programmation linéaire colorée comme l’ensemble des questions algorithmiques liées au théorème de Carathéodory coloré. Parmi ces questions, deux ont particulièrement retenu notre attention. La première concerne la complexité du calcul d’un sous-ensemble arc-en-ciel comme dans l’énoncé du théorème. La seconde, en un sens plus générale, concerne la complexité du problème de décision suivant. Etant donnés des ensembles de points dans Rd , correspondant aux couleurs, il s’agit de décider s’il existe un sous-ensemble arc-en-ciel contenant 0 dans son enveloppe convexe, et ce en dehors des conditions du théorème de Carathéodory coloré. L’objectif de cette thèse est de mieux délimiter les cas polynomiaux et les cas “difficiles” de la programmation linéaire colorée. Nous présentons de nouveaux résultats de complexités permettant effectivement de réduire l’ensemble des cas encore incertains. En particulier, des versions combinatoires du théorème de Carathéodory coloré sont présentées d’un point de vue algorithmique. D’autre part, nous montrons que le problème de calcul d’un équilibre de Nash dans un jeu bimatriciel peut être réduit polynomialement à la programmation linéaire coloré. En prouvant ce dernier résultat, nous montrons aussi comment l’appartenance des problèmes de complémentarité à la classe PPAD peut être obtenue à l’aide du lemme de Sperner. Enfin, nous proposons une variante de l’algorithme de Bárány et Onn, calculant un sous ensemble arc-en-ciel contenant 0 dans son enveloppe convexe sous les conditions du théorème de Carathéodory coloré. Notre algorithme est clairement relié à l’algorithme du simplexe. Après une légère modification, il coïncide également avec l’algorithme de Lemke, calculant un équilibre de Nash dans un jeu bimatriciel. La question combinatoire posée par le théorème de Carathéodory coloré concerne le nombre de sous-ensemble arc-en-ciel contenant 0 dans leurs enveloppes convexes. Deza, Huang, Stephen et Terlaky (Colourful simplicial depth, Discrete Comput. Geom., 35, 597–604 (2006)) ont formulé la conjecture suivante. Si jSi j Æ d Å1 pour tout i 2 {1, . . . ,d Å1}, alors il y a au moins d2Å1 sous-ensemble arc-en-ciel contenant 0 dans leurs enveloppes convexes. Nous prouvons cette conjecture à l’aide d’objets combinatoires, connus sous le nom de systèmes octaédriques, dont nous présentons une étude plus approfondie / The colorful Carathéodory theorem, proved by Bárány in 1982, states the following. Given d Å1 sets of points S1, . . . ,SdÅ1 µ Rd , each of them containing 0 in its convex hull, there exists a colorful set T containing 0 in its convex hull, i.e. a set T µ SdÅ1 iÆ1 Si such that jT \Si j • 1 for all i and such that 0 2 conv(T ). This result gave birth to several questions, some algorithmic and some more combinatorial. This thesis provides answers on both aspects. The algorithmic questions raised by the colorful Carathéodory theorem concern, among other things, the complexity of finding a colorful set under the condition of the theorem, and more generally of deciding whether there exists such a colorful set when the condition is not satisfied. In 1997, Bárány and Onn defined colorful linear programming as algorithmic questions related to the colorful Carathéodory theorem. The two questions we just mentioned come under colorful linear programming. This thesis aims at determining which are the polynomial cases of colorful linear programming and which are the harder ones. New complexity results are obtained, refining the sets of undetermined cases. In particular, we discuss some combinatorial versions of the colorful Carathéodory theorem from an algorithmic point of view. Furthermore, we show that computing a Nash equilibrium in a bimatrix game is polynomially reducible to a colorful linear programming problem. On our track, we found a new way to prove that a complementarity problem belongs to the PPAD class with the help of Sperner’s lemma. Finally, we present a variant of the “Bárány-Onn” algorithm, which is an algorithmcomputing a colorful set T containing 0 in its convex hull whose existence is ensured by the colorful Carathéodory theorem. Our algorithm makes a clear connection with the simplex algorithm. After a slight modification, it also coincides with the Lemke method, which computes a Nash equilibriumin a bimatrix game. The combinatorial question raised by the colorful Carathéodory theorem concerns the number of positively dependent colorful sets. Deza, Huang, Stephen, and Terlaky (Colourful simplicial depth, Discrete Comput. Geom., 35, 597–604 (2006)) conjectured that, when jSi j Æ d Å1 for all i 2 {1, . . . ,d Å1}, there are always at least d2Å1 colourful sets containing 0 in their convex hulls. We prove this conjecture with the help of combinatorial objects, known as the octahedral systems. Moreover, we provide a thorough study of these objects

<p>This thesis deals with combinatorial and geometric aspects of linear optimization, and consists of two parts.</p> <p>In the first part, we address a conjecture formulated in 2008 and stating that the largest possible average diameter of a bounded cell of a simple hyperplane arrangement of n hyperplanes in dimension d is not greater than the dimension d. The average diameter is the sum of the diameters of each bounded cell divided by the total number of bounded cells, and then we consider the largest possible average diameter over all simple hyperplane arrangements. This quantity can be considered as an indication of the average complexity of simplex methods for linear optimization. Previous results in dimensions 2 and 3 suggested that a specific type of extensions, namely the covering extensions, of the cyclic arrangement might achieve the largest average diameter. We introduce a method for enumerating the covering extensions of an arrangement, and show that covering extensions of the cyclic arrangement are not always among the ones achieving the largest diameter.</p> <p>The software tool we have developed for oriented matroids computation is used to exhibit a counterexample to the hypothesized minimum number of external facets of a simple arrangement of n hyperplanes in dimension d; i.e. facets belonging to exactly one bounded cell of a simple arrangement. We determine the largest possible average diameter, and verify the conjectured upper bound, in dimensions 3 and 4 for arrangements defined by no more than 8 hyperplanes via the associated uniform oriented matroids formulation. In addition, these new results substantiate the hypothesis that the largest average diameter is achieved by an arrangement minimizing the number of external facets.</p> <p>The second part focuses on the colourful simplicial depth, i.e. the number of colourful simplices in a colourful point configuration. This question is closely related to the colourful linear programming problem. We show that any point in the convex hull of each of (d+1) sets of (d+1) points in general position in R^d is contained in at least (d+1)²/2 simplices with one vertex from each set. This improves the previously established lower bounds for d>=4 due to Barany in 1982, Deza et al in 2006, Barany and Matousek in 2007, and Stephen and Thomas in 2008.</p> <p>We also introduce the notion of octahedral system as a combinatorial generalization of the set of colourful simplices. Configurations of low colourful simplicial depth correspond to systems with small cardinalities. This construction is used to find lower bounds computationally for the minimum colourful simplicial depth of a configuration, and, for a relaxed version of the colourful depth, to provide a simple proof of minimality.</p> / Doctor of Philosophy (PhD)

L'objectif de cette thèse était de démontrer les potentialités de l'impression à jet d'encre pour le pilotage d'une HLED contenant des clusters métalliques phosphorescents dans le rouges, par des transistors organiques à effet de champs. Pour atteindre ce but, le projet a été divisé en deux parties : I) La fabrication et l'optimisation de transistors organiques de type n par photolithographie puis le transfert technologique vers l'impression à jet d'encre. II) Parallèlement au développement des transistors, je me suis attaché à la conception de matériaux hybrides luminescents pour la réalisation d'HLED. Pour la partie transistor, nous avons obtenu une meilleure compréhension des facteurs influençant l'injection de charges mais aussi la stabilité électrique pour un transistor de géométrie grille basse/contacts bas avec le fullerène C60 évaporé. Nous avons démontré que la résistance de contact est d'une part gouvernée par la morphologie du SCO au niveau des électrodes et d'autre part indépendante du travail de sortie du métal. En outre, nous avons vu que la stabilité électrique des transistors est fortement impactée par la nature du contact source et drain. L'optimisation des transistors fabriqués par photolithographie, qui a essentiellement consisté à modifier les interfaces, nous a permis de développer des transistors de type n performants avec des mobilités à effet de champ saturées allant jusqu'à 1,5 cm2/V.s pour une température maximum de procédé de 115 °C. Le transfert vers un transistor fabriqué par impression à jet d'encre a ensuite été effectué. Nous avons ensuite démontré que les morphologies de l'électrode de grille et de l'isolant, fabriqués par impression à jet d'encre, ont un impact négligeable sur les performances des transistors. Pour notre structure imprimée, l'injection de charges aux électrodes S/D est en fait le facteur clé pour la réalisation de transistors performants. Finalement, des matériaux phosphorescents rouges à base de cluster métalliques octaédrique de molybdène ont été développés. Le copolymère hybride résultant présentait un rendement quantique de photoluminescence de 51 %. La réalisation de l'HLED a ensuite été effectuée par combinaison d'une LED bleue commercial et du copolymère dopé avec des clusters octaédriques de molybdène pour des applications possibles en biologie ou dans l'éclairage. / The objective of this thesis was to demonstrate the potentialities of inkjet printing for driving an HLED containing red phosphorescent metallic clusters, with organic field effect transistors. To achieve this goal, the project was divided into two parts: I) The fabrication and optimization of n-type organic transistors by photolithography and then transfer to inkjet printing. II) Parallel to the development of transistors, I focused on designing luminescent hybrid materials for HLED realization. Concerning transistors, we obtained a better understanding of the factors influencing the charge injection but also the electrical stability for bottom gate/ bottom contact geometry transistor with evaporated C60 semiconductor. We have demonstrated that the contact resistance is on the one hand governed by the morphology of the SCO at the electrodes and on the other hand independent of the metal work function. In addition, we have observed that transistors electrical stability of is strongly impacted by the source and drain contact nature. The optimization of photolithography transistors, which essentially consisted of modifying the interfaces, allowed us to develop efficient n-type transistors with saturated field effect mobilities of up to 1.5 cm2/V.s for a maximal process temperature of 115 °C. The technological transfer to inkjet printed transistors was then performed. We then demonstrated that gate electrode and insulator morphologies deposited by inkjet printing, have a negligible impact on transistors performances. For our printed structure, charges injection at the S/D electrodes is in fact the key factor for high performance transistors realization. Finally, red phosphorescent materials based on molybdenum octahedral metal cluster have been developed. The resulting hybrid copolymer showed photoluminescence quantum yield up to 51%. The realization of the HLED was then carried out by combining a commercial blue LED and the copolymer doped with octahedral molybdenum clusters for possible applications in biology or lighting.