京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21783号 / 工博第4600号 / 新制||工||1717(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Interactions of Asthma Drugs with Artificial Saliva and Mucus. Modeling pulmonary particulate transport requires related biofluid physicochemical properties. Aims included measuring the effects of common aerosol drugs on artificial saliva and diffusivities of asthma medications in mucus. Artificial saliva solutions doped with asthma medications were characterized by pH, interfacial tension, and rheology. To measure diffusion, drug concentration was monitored by time-dependent FTIR spectra, and diffusivity obtained using Fick¡¦s second law. Measured theophylline and albuterol diffusivities were ca. 10-6 cm2/s. Surface Modification of Polymer Films with Light-Emitting Chemicals. To develop a polymer film system that changed color in response to radiation, acid groups of poly(ethylene-co-acrylic acid) were used to attach two light-emitting polymers: 4„S-(octyloxy)-4-biphenylcarboxylic acid and 2,7-bis(bromomethyl)-9,9-dihexyl-9Hluorene. Each reaction step was confirmed using static contact angle goniometry, FTIR spectroscopy, and X-ray photoelectron spectroscopy. UV-Vis and fluorescence spectroscopy measured the absorption spectra. Modified films were irradiated (ƒÜ=254 nm) and produced blue emissions.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24616号 / 工博第5122号 / 新制||工||1979(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 奥田 浩司, 教授 中村 裕之 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Bridge engineers and managers in coastal areas and cold regions frequently specify the application of surface treatments on concrete bridge decks as barriers against chloride ingress. In consideration of concrete cover thickness and the presence of stay-in-place metal forms (SIPMFs), the objective of this research was to determine the latest timing of initial surface treatment applications on concrete bridge decks subjected to external chloride loading before chlorides accumulate in sufficient quantities to initiate corrosion during the service life of the deck. Chloride concentration data for this research were collected from 12 concrete bridge decks located within the I-215 corridor in Salt Lake City, Utah. Numerical modeling was utilized to generate a chloride loading function and to determine the diffusion coefficient of each deck. Based on average diffusion coefficients for decks with and without SIPMFs, chloride concentration profiles were computed through time for cover thicknesses of 2.0 in., 2.5 in., and 3.0 in. The results of the work show that the average diffusion coefficient for bridge decks with SIPMFs is approximately twice that of decks without SIPMFs and that, on average, each additional 0.5 in. of cover beyond 2.0 in. allows an extra 2 years for decks with SIPMFs and 5 years for decks without SIPMFs before a surface treatment must be placed to prevent excessive accumulation of chlorides. Although the data generated in this research are based on conditions typical of bridge decks in Utah, they clearly illustrate the effect of cover depth and the presence of SIPMFs. Given these research findings, engineers should carefully determine the appropriate timing for initial applications of surface treatments to concrete bridge decks in consideration of cover depth and the presence of SIPMFs. For maintenance of concrete bridge decks with properties similar to those tested in this study, engineers should follow the guidelines developed in this research to minimize the ingress of chlorides into the decks over time and therefore retard the onset of reinforcement corrosion; altogether separate guidelines may be needed for decks having substantially different properties. Surface treatments should be replaced as needed to ensure continuing protection of the concrete bridge deck against chloride ingress.

Hot section components in gas turbines can be NiCoCrAlY-coated to provide the component with an Al reservoir that maintains a protective oxide layer on its surface. Over the service life of the component, the coatings degrade by composition and phase changes due to oxidation/hot-corrosion, and multicomponent interdiffusion from and into the superalloy substrate. In this study, the rate of Al interdiffusion into selected Ni-base superalloys using various diffusion couples of two-phase NiCoCrAlY (beta + gamma) and single beta-phase NiAl with the selected alloys is measured. The diffusion couples were examined with an emphasis on the composition-dependence of Al interdiffusion. Microstructural analysis of the NiCoCrAlY vs. superalloys couples is performed to examine the dependence of coatings lifetime on the superalloy composition. The beta-NiAl diffusion couples were analyzed to determine the integrated, apparent and average effective interdiffusion coefficient as a function of superalloy's composition. Concentration profiles were obtained by EPMA of the NiAl vs. superalloy diffusion couples. Findings of this study show that the lifetimes of NiCoCrAlY are heavily dependent on superalloy compositions. The rate of interdiffusion in the diffusion couples is affected by the refractory precipitate phase microstructure structures in the interdiffusion zones as well as by component interactions. The results of the beta-NiAl diffusion couples show that increasing concentrations of Cr, Mo and Ti in the superalloy increase the Al effective interdiffusion coefficient into the superalloy, while increasing concentrations of Al, Ta and W reduce it. Thus NiCoCrAlY-superalloy systems may be designed to produce optimal microstructures in the interdiffusion zone and minimize Al interdiffusion by consideration of these diffusional interactions.

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This study has two parts. In the first part we develop a computational approach to the solution of an inverse modelling problem concerning the material properties of electrolytes used in Lithium-ion batteries. The dependence of the diffusion coefficient and the transference number on the concentration of Lithium ions is reconstructed based on the concentration data obtained from an in-situ NMR imaging experiment. This experiment is modelled by a system of 1D time-dependent Partial Differential Equations (PDE) describing the evolution of the concentration of Lithium ions with prescribed initial concentration and fluxes at the boundary. The material properties that appear in this model are reconstructed by solving a variational optimization problem in which the least-square error between the experimental and simulated concentration values is minimized. The uncertainty of the reconstruction is characterized by assuming that the material properties are random variables and their probability distribution estimated using a novel combination of Monte-Carlo approach and Bayesian statistics. In the second part of this study, we carefully analyze a number of secondary effects such as ion pairing and dendrite growth that may influence the estimation of the material properties and develop mathematical models to include these effects. We then use reconstructions of material properties based on inverse modelling along with their uncertainty estimates as a framework to validate or invalidate the models. The significance of certain secondary effects is assessed based on the influence they have on the reconstructed material properties. / Thesis / Doctor of Philosophy (PhD)

Karst landscapes can serve as carbon sinks when carbon dioxide (CO2) reacts with water to form carbonic acid, which then weathers carbonate rocks. However, CO2 can also move through the subsurface via gas diffusion, a process that is not well-understood in karst systems. This study focused on quantifying CO2 diffusion within a karst sinkhole. The objectives of this study were to: 1) identify the depth of the zero-flux plane (i.e., depths of local maximum CO2 concentrations), analyze the distributions of concentration gradients, and investigate the validity of a uniform concentration gradient throughout the profile; and 2) assess the influences of vertical position and seasonality on CO2 fluxes within this sinkhole. The study site contained three locations within the sinkhole, including shoulder, backslope, and toeslope locations. Each location had three soil CO2 and three soil water content/temperature sensors placed at 20, 40, and 60 cm depths. Zero-flux planes were seldom detectable during the warm season (April-September) but were frequently found near the surface (20 or 40 cm) during the cool season (October-March). The common assumption of a uniform concentration gradient was often invalid based on relative concentrations between sensor pairs. As for the second objective, CO2 fluxes generally followed a trend of upward fluxes in warmer months that was partially offset by downward fluxes during the cooler months. These study results provide new insight into CO2 dynamics in a karst system, and suggest that subsurface processes such as chemical weathering and cave ventilation affect the direction and magnitude of CO2 fluxes. / Master of Science / Carbon dioxide (CO2) within soils is a larger pool of CO2 than atmospheric CO2. Therefore, the movement of CO2 within soils is important to understand, as soil CO2 may eventually diffuse through the soil and into the atmosphere. Soil CO2 movement is dependent on many factors such as soil water content, porosity, and temperature. Soil CO2 movement may vary between landscapes as well, due to chemical weathering processes being sinks of soil and atmospheric CO2. One type of important landscape is karst, which can be identified by easily soluble rocks, usually in the forms of limestone and dolomite rocks. In order to investigate the influences of karst landscapes on the movement of soil CO2, in this study I identified the depths of CO2 maximum concentrations and CO2 movement over time and by sinkhole slope position. The results from this study were that the depth of maximum CO2 concentration was deeper, > 40 cm, during the warmer months and often shallower, ≤ 40 cm, during the cooler months. The CO2 fluxes generally followed a trend of upward fluxes in warmer months that was partially offset by downward fluxes during the cooler months. The results from this study suggest that due to vertical differences in soil properties, temperature, chemical weathering of the karst rock, and cave ventilation the depth of the maximum CO2 concentration and the CO2 movement vary by season and sinkhole slope location. This study provides new insight to CO2 movement relative to karst landscapes while highlighting the importance of soil and geologic properties as influences that can alter the direction and magnitude of CO2 fluxes.