Although fluoride is used at low concentrations in drinking water as a means of promoting dental health, it poses a danger at high exposure levels where it can lead to skeletal fluorosis or other adverse effects. Cyanide is notoriously toxic, and its large scale use in industrial processes warrants the need for close monitoring to remain aware of potential contamination of water sources and other environmental resources. Based on these considerations, it is critical to continue to develop improved methods of monitoring fluoride and cyanide concentrations in water. However, molecular recognition of these anions in water poses considerable challenges. For fluoride, this is due largely to its high hydration enthalpy (Ho = -504 kJ mol-1), which drastically reduces its reactivity in water. Additionally, the strong basicity of cyanide (pKa of (HCN) = 9.3) may obscure its detection in neutral water due to protonation. In addition to achieving detection of these anions in water, it is most desirable to have information of the detection event relayed in the form of a positive, rather than negative, response (i.e., turn-on vs turn-off). The general strategy of appending cationic groups to triarylboranes imparts beneficial Coulombic, inductive, and sometimes chelate effects that have allowed a number of these Lewis acidic receptors to sense fluoride and cyanide in aqueous environments. With the goal of developing new triarylborane-based receptors that show enhanced affinities for these anions, as well as turn-on responses to detection, a series of pyridinium boranes were synthesized and studied. Having recognized that the inherent Lewis acidity of antimony(V) species might be exploited for anion sensing, we also describe initial studies on the ability of tetraorganostibonium ions (R4Sb+) and cationic transition metal-triarylstibine complexes (R3SbM+) to complex fluoride. Finally, the electropositivity of antimony and its ability to form stable compounds in both the +3 and +5 oxidation states have led us to begin investigations into the bonding and redox reactivity of novel metal stibine/stiborane complexes.

The spectroscopy of wide-bandgap fluoride materials doped with divalent ytterbium is presented. The structure of impurity-trapped excitons is explored, vacuum ultraviolet excitation is used to investigate the transfer processes between excitations, and the effect of confinement on self-trapped excitons is studied. The excited-state structure of impurity-trapped excitons is measured in the multisite system NaMgF₃:Yb²⁺. A two-colour ultraviolet-infrared pulsed photoluminescence enhancement technique is employed to probe the interlevel transitions and dynamics of impurity-trapped excitons in doped insulating phosphor materials. NaMgF₃:Yb²⁺ exhibits emission from two charge-compensation centres with peaks at 22 300 cm⁻¹ (448 nm) and 24 000 cm⁻¹ (417 nm). The observed photoluminescence enhancement is caused by a combination of intra-excitonic excitation and electron trap liberation. The electron traps are inferred to have a depth of approximately 800 cm⁻¹. Time-resolved VUV spectroscopic studies of emission and excitation spectra of CaF₂:Yb, NaMgF₃Yb and MgF₂:Yb are presented to investigate excitation and relaxation mechanisms of both impurity-trapped excitons and intrinsic excitons in each fluoride host. Host-to-impurity energy transfer mechanisms leading to formation of impurity-trapped excitons are discussed. The 4f¹⁴ → 4f¹³5d CaF₂:Yb²⁺ absorption bands are successfully modeled with a semi-empirical effective Hamiltonian calculation for NaMgF₃:Yb²⁺ and MgF₂:Yb²⁺. The excitation and emission spectra of all studied materials are compared. Results on VUV spectroscopy of 3 and 5 monolayer CdF₂–CaF₂ superlattices show the change in optical behaviour of the self-trapped exciton in CdF₂ when it is confined and give an indication of the radius of the exciton. The decay of the emission is modeled with three components, corresponding to three self-trapped exciton states. Results on the VUV spectroscopy of CdF₂–CaF₂ superlattices show that the confinement effect seems to equally influence the energy of excitonic and bandgap absorption in 3 and 5 monolayer superlattices. At the same time, as the self-trapped exciton is more confined, the emission is blue-shifted by 1600 cm⁻¹ indicating that the effective excitonic radius is about three monolayers.

In this study, membranes were made from three polyvinylidene fluoride (PVDF) polymers individually and the blend systems of high (H) and low (L) molecular weight PVDF by phase inversion process. After investigating membrane casting solutions’ viscous and thermodynamic properties, the membranes so fabricated were characterized by scanning electron microscopy, gas permeation tests, porosity measurement, contact angle (CA) and liquid entry pressure of water (LEPw) measurement, and further subjected to vacuum membrane distillation (VMD) in a scenario that was applicable for cooling processes, where the feed water temperature was maintained at 27℃. It was found that PVDF solutions’ viscosities and thermodynamic instabilities were determined by the types of PVDF employed in single polymer systems and the mixing ratios of two PVDF polymers in blend systems. Thus the membrane properties and performances were influenced by the aforesaid factors as well. In single polymer systems, it was found that the membrane surface roughness and porosity increased with an increase in molecular weight. Among all the membranes casted in this study, the water vapor flux of VMD was found to be the highest at the intermediate range of H:L ratio, i.e., 4:6, at which the thickness of the sponge-like layer showed a minimum, the finger-like macro-voids formed a more orderly single-layer structure, and the LEPw showed a minimum. A conclusion can be made that blend systems of high molecular weight PVDF polymers and low molecular weight PVDF polymers could be used to optimize membrane performance in vacuum membrane distillation.

This thesis undertakes a complete reinvestigation of the archaeology of a large Early Bronze Age cemetery at İkiztepe in northern Turkey, by utilizing oxygen and strontium isotope analysis of human remains in combination with spatial and biodistance analysis and various dating techniques to identify potential immigrants to the site and to examine larger issues of residential mobility and social organization. The occupation of the Northern Anatolian site of İkiztepe is traditionally assigned to the Late Chalcolithic and Early Bronze Ages. However, the site’s chronological framework has been challenged in recent years. These chronological issues have been addressed by applying fluoride and AMS radiocarbon dating to the skeletal remains from the İkiztepe cemetery, to develop an absolute and relative chronology for the burials. These results have shown that the cemetery dates at least a millennium earlier than previously supposed. Oxygen and strontium isotope analyses allowed the identification of individuals whose bone chemistry suggests that they were possible long distance immigrants to the site of İkiztepe, as well as suggesting the existence of a group of mobile individuals who may represent a transhumant segment of the İkiztepe population. Spatial and biodistance analyses suggest that principles of cemetery organization in this period were highly complex. Immigrant individuals and nomadic or semi-nomadic segments of the population do not appear to have been distinguished in any observable way from their sedentary local counterparts, displaying similar burial types, grave goods and spatial locations. Furthermore, burial within the İkiztepe cemetery does not appear to have been kin structured. These results suggest that assumptions about funerary practices as important indicators of cultural identity and lineage affiliation may represent an over-simplification of complex patterns of interaction and integration among and within populations and cultural groups.

The ultimate goal of this study is to examine the feasibility of extracting silicon from silica through electrolysis. The objective of the thesis was to evaluate the physico-chemical properties of a cryolite-lithium fluoride mixture as an electrolyte for the electrolysis process. A study of 86.2wt%Cryolite and13.8wt%Lithium fluoride melt with silica concentration varying from 0-4wt% and temperature range of 900-1000°C was done. Three properties were measured using two sets of experiments: 1) Dissolution Behaviour Determination, to obtain a) solubility limit, b) dissolution rate (mass transfer coefficient) and 2) density using Archimedes’ Principle. The study concluded that solubility and dissolution rate increases with temperature and the addition of LiF to cryolite decreases the solubility limit but increases the rate at which silica dissolves into the melt. With addition of silica, the apparent density of electrolyte first increases up to 2-3wt% and the drops.

The ultimate goal of this study is to examine the feasibility of extracting silicon from silica through electrolysis. The objective of the thesis was to evaluate the physico-chemical properties of a cryolite-lithium fluoride mixture as an electrolyte for the electrolysis process. A study of 86.2wt%Cryolite and13.8wt%Lithium fluoride melt with silica concentration varying from 0-4wt% and temperature range of 900-1000°C was done. Three properties were measured using two sets of experiments: 1) Dissolution Behaviour Determination, to obtain a) solubility limit, b) dissolution rate (mass transfer coefficient) and 2) density using Archimedes’ Principle. The study concluded that solubility and dissolution rate increases with temperature and the addition of LiF to cryolite decreases the solubility limit but increases the rate at which silica dissolves into the melt. With addition of silica, the apparent density of electrolyte first increases up to 2-3wt% and the drops.

A new class of polymer coated lanthanide fluoride nanoparticle aggregates (NPAs) was developed as potential MRI contrast agents. The NPA synthesis has been perfected to control the size distribution and optimize relaxivities. Polyacrylic acid was used as a stabilizing polymer, and was conjugated to folic acid to improve targeting to SK-BR-3 breast cancer cells. Terbium was incorporated in the synthesis to study the passive and active targeting properties of NPAs. Through a series of microscopy experiments, a significant difference in uptake between NPAs with and without targeting moieties occurs after 48 hours of incubation. The relaxivity of the optimized nanoparticles was measured to be 56 s-1(mg/ml)-1 using a 1.5 T scanner, which may be compared to that of the commercially available Gd3+-DTPA [R1 = 7 s-1(mg/ml)-1]. Abdominal perfusion studies in rats also demonstrated that the NPAs provide better contrast of the vasculature than Gd3+-DTPA does at the same mass concentration.

The present research focuses on the coupling of mechanical and electrical properties of materials and culminates in a direct connection between applied strain to thin-films, thin-film electron binding energy, the energy loss via plastic deformation provided by an indentation, and the substrate resistance. The methods used in this research include X-ray photoelectron spectroscopy (XPS), nanoindentation, digital optical microscopy, and sputter coat deposition. It is discovered that there is a shift in electron binding energy on the scale of 0.2 eV to 1.4 eV in gold and palladium thin-films sputtered on polyvinylidene fluoride (PVDF) through the application of strain induced by a convex shape. There is a change in the area beneath the load-displacement curve measured via indentation from 5.55 x 10^-10 J to 4.78 x 10^-10 J when the gold-palladium thin-film sputtered on PVDF is changed from the flat arrangement to the convex arrangement. Furthermore, the strain also changed the electrical resistance of aluminum foil, which indicates that the substrate electrical resistance is affected by the induced strain. The internal resistance of a circuit developed for this research changed from 7.76 ohms for flat samples to 8.03 ohms and 8.33 ohms for flat and convex samples, respectively. It is expected that the research can be used to estimate the strain in nanogears and other devices at small length scales.

The need for industrial gas turbines to operate at higher temperatures and/or speeds has resulted in the continual modification of nickel-based superalloys to provide better high-temperature strength and corrosion resistance for components such as hot-section turbine blades. Thermal-Mechanical Fatigue (TMF) cracking, accelerated by the oxidation that forms as a result of the exposure of bare metal during the crack-opening stages, is one of the most common forms of damage experienced by service-run turbine blades. Due to the high costs associated with manufacturing nickel-based superalloy components, damaged turbine blades must be repaired to restore their original mechanical properties. One such method, Activated Diffusion Brazing (ADB), is under development for this purpose, and involves melting a two-part powder mixture into a damaged region. However, the tenacious oxides formed on nickel-based superalloy components provide an obstacle for the repair process, and must be removed. Fluoride-Ion Cleaning (FIC) uses flowing hydrogen and HF gas to remove tenacious oxide scales through a set of chemical reactions, leaving cleaned components free of oxide compounds and depleted of the strong oxide-formers of Al and Ti. GTD111 is a nickel-based superalloy containing the strong oxidizing elements of Al, Ti, and Cr, and is similar in composition to other nickel-based superalloys such as DD8 and Rene95. Literature concerning the oxidation, cleaning, and brazing of this particular alloy is limited, and as such this thesis serves as a comprehensive overview of the chemical effects of each above process on GTD111. The objectives of this project are to determine, through SEM-EDX and element mapping analysis, the oxidation behavior of nickel-based superalloy GTD111, the effects of oxidation and FIC on the chemistry near the surface of this particular alloy, and the effects of mixing ratio and paste viscosity on the quality of repairs made by ADB. Notches of 8 mm depth and 0.25 mm width were made in coupons of GTD111 via wire-EDM and samples were oxidized between 1 and 452 hours at 900°C. Samples oxidized between 96 and 452 hours were sectioned in half and one half of each sample was cleaned via the standard FIC process at Ti-Coating Inc. Notches of 8 mm depth and 1 mm width, also made via wire-EDM, were repaired by the ADB process with a bonding temperature of 1220°C and a holding time of 65 minutes. Time-dependent multi-layer oxide growth was observed on all samples, consisting of an innermost discontinuous aluminum oxide region, followed by a thin continuous band of Ni-W-Ta oxide and a thicker, very dense chromium oxide layer. Some oxidation times exhibited the presence of weak, inconsistent oxide regions rich in Ni and/or Ti. Since the GTD111 alloy does not contain sufficient amount of Al to form a continuous layer – as 5-7% Al is required – oxidation resistance was provided mainly by the formation of the dense chromium oxide layer. A region heavily depleted of Al and Ti and therefore the strengthening gamma prime phase was observed below and surrounding the Al-rich oxide regions. Chemical analysis of cleaned samples showed that the standard FIC process at Ti-Coating Inc. was able to remove all oxide compounds formed during oxidation at 900°C, and that the prior oxidation time had no effect on the chemistry within the surface of the cleaned samples; however, the depths of elemental and gamma prime phase depletion were affected. The elemental depletions of Al and Ti have been observed in past studies, but depletions of Ni and concentrations of Cr near the surfaces of cleaned components have not been previously observed. Preliminary brazing trials made with varying paste viscosities demonstrated the importance of paste pre-placement and maintaining the molten filler metal within the notch, as better pre-placement resulted in higher densities in the braze-repaired region of the brazing trial samples. Although porosity was observed on all samples, the paste pre-placement was found to be more important in reducing porosity than the mixing ratio and paste viscosity, although using an appropriate paste viscosity allowed for better pre-placement.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24003号 / エネ博第439号 / 新制||エネ||83(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 佐川 尚, 教授 野平 俊之 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM