The need for renewable and cleaner sources of energy has made biofuels an interesting alternative to fossil fuels, especially in the case of butanol isomers, with their favorable blend properties and low hygroscopicity. Although C4 alcohols are prospective fuels, some key reactions governing their pyrolysis and combustion have not been adequately studied, leading to incomplete kinetic models. Butanol reactions kinetics is poorly understood. Specifically, the unimolecular and H-assisted tautomerism of propen-2-ol to acetone, which are included in butanol combustion kinetic models, are assigned rate parameters based on the analogous unimolecular tautomerism vinyl alcohol ↔ acetaldehyde and H addition to the double bound of iso-butene, respectively. In an attempt to update current kinetic models for tert- and 2-butanol, a theoretical kinetic study of the unimolecular and H-assisted tautomerism, i-C3H5OH⟺CH3COCH3 and i-C3H5OH+Ḣ⟺CH3COCH3+Ḣ, was carried out by means of CCSD(T,FULL)/aug-cc-pVTZ//CCSD(T)/6-31+G(d,p) and CCSD(T)/aug-cc-pVTZ//M062X/cc-pVTZ ab initio calculations, respectively. For H-assisted tautomerism, the reaction takes place in two consecutive steps: i-C3H5OH+Ḣ⟺CH3ĊOHCH3 and CH3ĊOHCH3⟺CH3COCH3+Ḣ. Multistructural torsional anharmonicity and variational transition state theory were considered in a wide temperature and pressure range (200 K – 3000 K, 0.1 kPa – 108 kPa). It was observed that decreasing pressure leads to a decrease in rate constants, describing the expected falloff behavior for both isomerizations. Results for unimolecular tautomerism differ from vinyl alcohol ↔ acetaldehyde analogue reactions, which shows lower rate constant values. Tunneling turned out to be important, especially at low temperatures. Accordingly, pyrolysis simulations in a batch reactor for tert- and 2-butanol with computed unimolecular rate constants showed important differences in comparison with previous results, such as larger acetone yield and quicker propen-2-ol consumption. In the combustion and pyrolysis batch reactor simulations, using all the rate constants computed in this work, H-assisted reactions are limited because H radicals become abundant once the propen-2-ol has been consumed by other reactions, such as the non-catalyzed tautomerism i-C3H5OH⟺CH3COCH3, which becomes one of the main source of acetone. The intermediate radical (CH3ĊOHCH3) is formed exclusively from tert-butanol, with its concentration in 2-butanol oxidation being smaller because the secondary alcohol is unable to produce the radical directly. In all cases, the intermediate is converted effectively to acetone.

Cette thèse s'inscrit dans l'étude des sous-variétés minimales et à courbure moyenne constante et de l'influence de la géométrie de la variété ambiante sur les solutions de ce problème.Dans le premier chapitre, en suivant les idées de F. Almgren, on propose une généralisation de la notion d'hypersurface de courbure moyenne constante à toutes codimensions. En dimension n-k on définie les sous-variétés à courbure moyenne constante comme les points critiques de la fonctionnelle de k-volume des bords des variétés minimales de dimension k+1. On prouve l'existence dans une variété riemannienne compacte de dimension n de sous-variétés à courbure moyenne constante de codimension n-k pour tout k < n qui sont des perturbations des sphères géodésiques de petit volume.Dans le deuxième chapitre, on s'intéresse aux surfaces minimales à bords libres dans la boule unité de l'espace euclidien de dimension 3, c'est-à-dire aux surfaces minimales plongées dans la boule unité dont le bord rencontre la sphère unité orthogonalement. On démontre l'existence de deux famille géométriquement distinctes de telles surfaces qui sont indexées par un entier n assez grand, qui représente le nombre de composantes connexes du bord de ces surfaces. Nous donnons en particulier une deuxième preuve d'un résultat de A. Fraser et R. Schoen concernant l'existence de telles surfaces.Un des résultats fondamentaux de la théorie des surfaces à courbure moyenne constante est le théorème de Hopf qui affirme que les seules sphères topologiques à courbure moyenne constante dans l'espace euclidien de dimension 3 sont les sphères rondes. Dans le troisième chapitre, on propose une construction dans une variété riemannienne de dimension 3 d'une famille de sphères topologiques à courbure moyenne constante qui ne sont pas convexes et dont la courbure moyenne est très grande. / The subject of this thesis is the study of minimal and constant mean curvature submanifolds and of the influence of the geometry of the ambient manifold on the solutions of this problem.In the first chapter, following the ideas of F. Almgren, we propose a generalization of the notion of hypersurface with constant mean curvature to all codimensions. In codimension n-k we define constant mean curvature submanifolds as the critical points of the functional of the k - dimensional volume of the boundaries of k+1 - dimensional minimal submanifolds. We prove the existence in compact n-dimensional manifolds of n-k codimensional submanifolds with constant mean curvature for all k<n which are perturbations of geodesic spheres of small volume.In the second chapter, we consider free boundary minimal surfaces in the unit ball of the three dimensional Euclidean space, i.e. minimal surfaces embedded in the unit ball and which meet the unit sphere orthogonally. We prove the existence of two geometrically distinct families of such surfaces parametrized by an integer n large enough, which represents the number of the boundary components. In particular, we give an independent proof of the result of A. Fraser and R. Schoen concerning the existence of such surfaces.One of the fundamental results of the theory of constant mean curvature surfaces is the Hopf's theorem which asserts that the only topological spheres with constant mean curvature in the Euclidean 3-space are round spheres. In the third chapter, we propose a construction in a three dimensional Riemannian manifold of a family of nonconvex topological spheres with large constant mean curvature.

abstract: This study aims to address the deficiencies of the Marcus model of electron transfer (ET) and then provide modifications to the model. A confirmation of the inverted energy gap law, which is the cleanest verification so far, is presented for donor-acceptor complexes. In addition to the macroscopic properties of the solvent, the physical properties of the solvent are incorporated in the model via the microscopic solvation model. For the molecules studied in this dissertation, the rate constant first increases with cooling, in contrast to the prediction of the Arrhenius law, and then decreases at lower temperatures. Additionally, the polarizability of solute, which was not considered in the original Marcus theory, is included by the Q-model of ET. Through accounting for the polarizability of the reactants, the Q-model offers an important design principle for achieving high performance solar energy conversion materials. By means of the analytical Q-model of ET, it is shown that including molecular polarizability of C60 affects the reorganization energy and the activation barrier of ET reaction. The theory and Electrochemistry of Ferredoxin and Cytochrome c are also investigated. By providing a new formulation for reaction reorganization energy, a long-standing disconnect between the results of atomistic simulations and cyclic voltametery experiments is resolved. The significant role of polarizability of enzymes in reducing the activation energy of ET is discussed. The binding/unbinding of waters to the active site of Ferredoxin leads to non-Gaussian statistics of energy gap and result in a smaller activation energy of ET. Furthermore, the dielectric constant of water at the interface of neutral and charged C60 is studied. The dielectric constant is found to be in the range of 10 to 22 which is remarkably smaller compared to bulk water( 80). Moreover, the interfacial structural crossover and hydration thermodynamic of charged C60 in water is studied. Increasing the charge of the C60 molecule result in a dramatic structural transition in the hydration shell, which lead to increase in the population of dangling O-H bonds at the interface. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2019

abstract: I focus on algorithms that generate good sampling points for function approximation. In 1D, it is well known that polynomial interpolation using equispaced points is unstable. On the other hand, using Chebyshev nodes provides both stable and highly accurate points for polynomial interpolation. In higher dimensional complex regions, optimal sampling points are not known explicitly. This work presents robust algorithms that find good sampling points in complex regions for polynomial interpolation, least-squares, and radial basis function (RBF) methods. The quality of these nodes is measured using the Lebesgue constant. I will also consider optimal sampling for constrained optimization, used to solve PDEs, where boundary conditions must be imposed. Furthermore, I extend the scope of the problem to include finding near-optimal sampling points for high-order finite difference methods. These high-order finite difference methods can be implemented using either piecewise polynomials or RBFs. / Dissertation/Thesis / Doctoral Dissertation Mathematics 2019

Following stringent mandates from environmental regulatory authorities worldwide, various steps are being implemented to ensure clean combustion with minimum emissions, including fuel dilution, mild combustion and additives. Due to the need to understand combustion characteristics in primary applications (engines and turbines) with minimum emissions, the laminar burning velocity of natural gas has been measured with CO2 dilution and a wide range of blends with higher hydrocarbons. And because it has improved anti-knock quality to reduce greenhouse gas emissions (GHGE), the demand for oxygenated gasoline is now worldwide, making a compelling case for determining combustion behavior of oxygenated gasoline doped with hydrogen, ozone and carbon monoxide. The first section of this dissertation discusses dilution of methane with CO2 at elevated pressures, providing insight into comparative laminar burning characteristics in a wide range of equivalence ratios, particularly significant at elevated initial pressure. Utilizing CHEMKIN, a detailed kinetic study has been performed that explains the varying dependence on dilution ratio controlled by initial pressure. The second phase of this work reports the laminar burning velocity measurement of commercial gasoline. A TPRFE surrogate was used here to investigate burning characteristics and to provide detailed kinetic analysis of gasoline doped with additives (hydrogen, carbon monoxide and ozone). A study was also made of the behavior of gasoline with these additives in practical applications like engine and turbines. For this purpose, laminar burning velocity was measured at elevated pressures and temperatures, by varying the concentrations of synthetic EGR, and followed by measuring turbulent burning velocity at two turbulent intensities.

Indiana University-Purdue University Indianapolis (IUPUI) / A chemically reactive turbulent traversing hot-jet issued from a pre-chamber to a relatively long combustion chamber is experimentally investigated. The long combustion chamber represents a single channel of a wave rotor constant-volume combustor. The issued jet ignites the fuel-air mixture in the combustion chamber. Fuel-air mixtures are prepared with different hydrocarbon fuels of different reactivity, namely, methane, propane, methane-hydrogen blend, methane-propane blend and methane-argon blend. The jet acts as a rapid, distributed and moving source of ignition, traversing across one end of the long combustion chamber entrance, induces complex flow structures such as a train of counter rotating vortices that enhance turbulent mixing. In general, a stationary hot-jet ignition process lack these structures due to absence of the traversing motion. The ignition delay of the fuels and fuel blends are measured in order to obtain insights about constant-volume pressure-gain combustion process initiated by a moving source of ignition and also to glean useful data about design and operation of a wave rotor combustor. Reactive hot-jets are useful to ignite fuel-air mixtures in internal combustion engines and novel wave rotor combustors. A reactive hot-jet or puff of gas issued from a suitably designed pre-chamber can act as rapid, distributed and less polluting ignition source in internal combustion engines. Each cylinder of the engine is provided with its own pre-chamber. A wave rotor combustor has an array of circumferentially arranged channels on a rotating drum. Each channel acts as a constant-volume combustor and produces high pressure combustion products. Implementation of hot-jet igniter in a wave rotor combustor offers utilization of available high temperature and high pressure reactive combustion products residing in each of the wave rotor channels as a distributed source of ignition for other channels, thus requiring no special pre-chamber in ultimate implementation. Such reactive products or partially combusted and radical-laden gases can be issued from one or more channels to ignite the fuel-air mixture residing in another channel. Due to the rotation of the rotor channels, the issued hot-jet would have relative motion with respect to one end of the channels and traverse across it. This thesis aims to investigate the effects of jet traverse time experimentally on ignition delay along with other important factors that affect the hot-jet ignition process such as fuel reactivity, fuel-air mixture preparation quality and stratification and equivalence ratio. In this study, the traversing motion of the hot-jet at one end of the main combustion chamber is implemented by keeping the main combustion chamber stationary and rotating a pre-chamber at speeds of 400 RPM, 800 RPM and 1200 RPM. The rotational speeds correspond to jet traverse times of 16.9 ms, 8.4 ms and 5.6 ms respectively. The fuel-air mixture inside the channel is at room temperature and pressure initially and its equivalence ratio is varied from 0.4 to 1.3. The cylindrical pre-chamber is initially filled with a 50%-50% methane-hydrogen blend fuel and air mixture at room pressure and temperature and at an equivalence ratio of 1.1. These conditions were chosen based on prior evidence of ignition rapidity with the jet properties. The hot-jet is issued by rupturing a thin diaphragm isolating the chambers. Using high frequency dynamic pressure transducer pressure histories, the diaphragm rupture moment and onset of ignition is measured. Pressure traces from two transducers are employed to measure the initial rupture shock speed and ignition delay. Schlieren images recorded by a high speed camera are used to identify ignition moment and validate the measured ignition delay times. Ignition delay is defined as time interval from the rupture moment to onset of ignition of fuel-air mixture in the main combustion chamber. The ignition system is designed to produce diaphragm rupture at almost exactly the moment when jet traverse begins. Ignition delay times are measured for methane, propane, methane-hydrogen blends, methane-propane blend and methane-argon blend. The equivalence ratio of the fuel-air mixtures varied from 0.4 to 1.3 in steps of 0.1 for stationary-hot jet ignition experiments and in steps of 0.3 for traversing hot-jet ignition experiments. Hot-jet ignition delay of fuel-air mixtures, for both stationary hot-jet ignition process and traversing hot-jet ignition process, generally increased with increasing equivalence ratio. For stationary hot-jet ignition delay, the minimum ignition delay occurs between Ф = 0.4 to Ф = 0.6 for the tested fuel-air mixtures. Both stationary and traversing hot-jet ignition delay depended on fuel reactivity. In particular, the shortest ignition delay times were observed for a fuel blend containing hydrogen. Among pure fuels propane exhibited slightly shorter ignition delay times, on average, compared to pure methane fuel. The addition of argon to pure methane, intended to control fuel density and buoyancy, increased the ignition delay. The traversing hot-jet ignition delay generally increased with increasing jet traverse times. To explain the variations in the measured hot-jet ignition delay and investigate qualitatively the effect of buoyancy on flame propagation and mixture stratification, the fuel-air mixture inside the main combustion chamber was ignited using a spark plug to generate a propagating laminar flame. The laminar flame propagated within the flammable regions of the channel in ways that sensitively reveal variations in local fuel-air mixture equivalence ratio. Flame luminosity images from a high speed camera and schlieren images revealed the fuel-air mixture being highly stratified depending on the density difference between the fuel and air and provided mixing time (0 s, 10s ,30s for most fuels). The lack of buoyancy-driven spreading caused the fuel to remain in the vicinity of the fuel injector resulting in significant longitudinal stratification of the fuel-air mixture. Lighter fuels stratified to the top of the chambers and heavier fuel stratified to the bottom of the chamber. Increasing the mixing time, which is defined as the time interval from end of fuel injection into the chamber to the triggering of the spark plug, improved the buoyancy-driven spreading and extended the flammable region as evidenced by the schlieren and flame luminosity images. The maximum pressure developed in the combustor for the three ignition processes, namely, stationary hot-jet ignition, traversing hot-jet ignition and spark ignition process in laminar flame propagation experiments were compared. Stationary hot-jet ignition process generally exhibited the highest pressure being developed in the chamber. Variations in heat loss, fuel-air mixture leakage and mass addition mechanisms reduced the maximum pressure for spark ignition and traversing hot-jet ignition process.

The influence of various pressure-less heating schedules (CRH - Constant Rate of Heating, TSS - Two Step Sintering, RCS – Rate Controlled Sintering) on the final microstructure of cubic zirconia ceramics was studied in this master´s thesis. There were used nanopowders ZrO2 (stabilized with 8 mol.% Y2O3) with initial particle size 80 nm (TZ-8Y) and 140 nm (TZ-8YSB). Powders were cold isostatically pressed and pressure-less sintered in air by different heating regimes. It was found that for both studied materials the modification of conventional sintering (CRH) using lower sintering temperatures and longer sintering dwell times can result in samples with finer microstructure. For example, the sintering of TZ-8YSB ceramics at a relatively low temperature (1270 °C) but for very long time (60 h) led to ceramics with the same final density (99,25 % of theoretical density) and almost identical grains (1,31 m vs. 1,27 m) in compare with TSS (1440 °C/ 1290 °C/ 15 h). On the other hand, RCS method showed no positive effect on the microstructure of both materials in comparison with CRH method. The obtained results indicate that the microstructure of c-ZrO2 ceramics can be influenced rather in its third sintering stage (by CRH and TSS methods) than in the second sintering stage (by RCS method).

京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第20755号 / 医博第4285号 / 新制||医||1024(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 伊佐 正, 教授 宮本 享, 教授 井上 治久 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

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A novel microstrip patch antenna topology is presented for achieving a dual-band response with arbitrarily closely spaced resonances. This topology is based on a coupled transmission line structure in order to take advantage of the separation in propagation constants for parallel (even-mode) and anti-parallel (odd-mode) current modes. Applying a metamaterials inspired design approach, periodic reactive load­ings are used to design the underlying transmission line to have specific propagation constants necessary to realize a desired separation between two resonant frequencies. Using a single probe feed for a finite coupled line segment, both even-and odd-mode resonances can be excited to radiate efficiently at their respective design frequencies. The efficiency of the odd-mode radiation is enhanced by separating the two lines, while strong coupling is maintained by inserting a series of narrowly-separated thin loops between them. Several example resonant antenna designs, in the 2.45 GHz band, are presented. The directivities of these microstrip patch antennas are enhanced by optimizing the physical length of the resonant structure. For a resonant antenna obtained by cas­cading several unit cells of reactively loaded microstrip segments, dispersion analysis is employed for the unit-cell design. Maximum directivity is achieved by choosing the overall physical length to be slightly less than a half wavelength in free space at the design frequency. This gain optimization is applied to three coupled-line antennas, as well as a single resonance patch. Excellent agreement is observed between simulated and measured responses across all designs. The potential of loading the coupled line structure with active components is also explored. Varactor diodes are placed on coupled-line structures in two configurations. In one configuration, both resonant frequencies are affected. In the other configura­tion, only the odd-mode characteristics are reconfigured. In this way, the resonant frequency of either one or both modes can be adjusted by applying a DC bias voltage to the varactor diode loading elements. Two antennas, one employing each of these topologies, were designed and fabricated. Control of the resonant frequency over the predicted range through applying a bias voltage is observed with the fabricated prototypes.