It is particularly intriguing in the role of the solid-state dopants, which are not only responsible for the semiconductivity, but also the dielectric properties of BaTiO3 ceramics, e.g. CaO, MgO, Y2O3, CoO and MnO2 for EIA-X7R characteristics. We have chosen to investigate three important processing parameters, oxygen partial pressure (pO2) for sintering, and two alkali-earth-metal oxides, i.e. CaO and MgO for solid-state additives in order to study how microstructure and dielectric properties are determined by them. They are used in MLCC industry for the effect in attaining X7R characteristics and protecting against or improving for dc degradation. Apart from establishing the temperature-dependent dielectric properties, i.e. temperature-coefficient of capacitance (TCC), for both qualitative and quantitative analysis, crystalline phases in sintered ceramics of tetragonal mixed with cubic, orthorhombic and rhombohedral phases are studied using XRD and Raman spectroscopy. For microscopic studies, SEM and TEM techniques, e.g. CBED and LACBED, combined with EDS are used to study phases both in core-shell. We will examine and confirm the fidelity of whether core-shell grains are induced by chemical inhomogeneity, and more importantly, if the diffuse phase transition is caused by such microstructure with direct observations, as previous studies in perovskite-related ceramics, and crystalline phase determination for these grains. It is also an objective that we investigate why and how, by what mechanism, the chemically similar alkali-earth metal oxides should impart completely different (and indeed opposite) effect in protecting against dc degradation. Keywords: MLCC, dc degradation, DPT, Raman spectroscopy, electron microscopy.

A novel process which does not require the traditional Chemical Vapor Deposition (CVD) synthesis techniques and which works at temperatures lower than the conventional techniques was developed for synthesis of carbon nanotubes (CNT). The substrates used for this study involved MEMS (Micro Electrical Mechanical Systems) elements and passive elements. These were coated with Fullerene using Physical Vapor Deposition or through a solution in an organic solvent. Catalyst precursors were deposited on these Fullerene coated substrates using “wet processes”. These substrates were then heated using either the integrated microheaters or external heaters in an inert atmosphere to obtain CNT. Thus, in this process we tried to obviate the Chemical Vapor Deposition (CVD) process for synthesis of CNT (SWCNT and MWCNT). The synthesized CNT will be characterized using Scanning Electron Microscopy and Raman spectroscopy techniques. Also, conductivity measurements were carried out for the synthesized tubes using Dry (contact based) and Wet (electro-chemical) methods. This work also proves the concept for the feasibility for a portable hand held instrument for synthesis of CNT with tunable “on demand” chirality.

Thesis (Ph.D.)--City University of Hong Kong, 2009. / "Submitted to Department of Physics and Material Sciences in partial fulfillment of the requirements for the degree of Doctor of Philosophy." Includes bibliographical references (leaves 140-167)

Thesis (Ph. D.)--University of California, Riverside, 2009. / Includes abstract. Available via ProQuest Digital Dissertations. Title from first page of PDF file (viewed March 8, 2010). Includes bibliographical references (p. 59-64). Also issued in print.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1962. / Includes bibliographical references (p. 42-45).

Nanosecond time-resolved resonance Raman (ns-TR3) spectroscopy was used in this thesis to study the photoreduction reactions and the photochemistry of chloro-substituted benzophenone (ClBP) triplets. The 3-chlorobenzophenone (3-ClBP), 4-chlorobenzophenone (4-ClBP) and 4,4′-dichlorobenzophenone (4,4′-diClBP) triplets exhibit similar properties to the parent BP triplet. In isopropyl alcohol (IPA), the hydrogen abstraction reactions were observed for the 3-ClBP, 4-ClBP and 4,4′-diDlBP triplets. The diphenylketyl (DPK) radicals produced from the hydrogen abstraction reactions were observed and the recombination of the DPK and dimethylketyl radicals at the para-position was observed to form a light absorption transient (LAT) species. In MeCN:H2O/1:1 aqueous solutions, these DPK radicals were also observed but with a slower formation rate and the LAT species was produced by reaction with OH radicals. Density functional theory (DFT) calculations were employed to help identify the intermediates seen in the TR3 spectra and to help provide information about the vibrational motions of the molecules examined. The 2-Cl-DPK radical was also observed in the TR3 spectra obtained in an IPA solvent. However, the yield of the 2-Cl-DPK radical and the hydrogen abstraction rate was observed to be significantly lower than that of the other ClBP examined here under the same experimental conditions. The results DFT calculations show that the 2-chloro substituent changes the geometry and the electron density of the molecular orbitals of the BP triplet so that the 2-chloro substituent reduces the hydrogen abstraction ability the triplet state, which is different the hypothesis put forward by some previous studies that an electron-withdrawing group should increase the photoreduction ability of BP derivatives. Norfloxacin (NF) and Enoxacin (EN) are representative derivatives of Fluoroquinolones (FQ). There are four forms of NF and EN and these different forms can coexist in aqueous solutions. The UV-vis absorption and resonance Raman (RR) spectra of NF and EN have been obtained in neat acetonitrile (MeCN), MeCN:HClO4-H2O/1:1 (pH?1), MeCN:H2O/1:1 (pH?7.5) and MeCN:NaOH-H2O/1:1 (pH?13) solutions. The species observed in the spectra are assigned by comparison of the experimental spectra to the DFT calculated spectra and the vibrational modes are also described from the results of the DFT calculations. The absorption spectra of NF and EN obtained in MeCN:H2O/1:1 solutions show that some other species coexist with the tautomeric forms in the neutral aqueous solution. The RR spectra of the tautomeric forms of NF and EN were obtained by subtraction of the RR spectra of the neutral and anionic forms from the RR spectra of NF and EN in neutral aqueous solutions. The results suggest that NF and EN exists in neutral, anionic and tautomeric forms in neutral aqueous solutions. The time dependant DFT calculation results suggest that the fluorine atom has little contribution to the lowest unoccupied molecular orbitals of the different forms of NF and EN. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Vanadium and molybdenum oxide catalysts have been prepared on different Ti02 supports by a variety of methods. Solutions of VOC13, VO(O'Bu)3 and MoOC14 were used to graft VOX and MoOX monolayers onto the supports in a single treatment. The other methods were intended to produce more than one monolayer (i. e. aqueous impregnation and multiple treatments of VOC13 and VO(O1Bu)3 ). TPR and Raman spectroscopy showed the formation above the monolayer of a phase denoted as disordered vanadium oxide, which has the same reducibility as the monolayer species but which has a band in the Raman spectrum at 995 cm-l. Raman spectroscopy also showed the formation of a disordered molybdenum oxide phase. With supports which contained phosphorus and potassium as impurities, TPR and Raman spectoscopy indicated a potassium-containing vanadium oxide, which was difficult to reduce and which showed no band at 995 cm-1. "Paracrystalline" V205 and MoO3 are formed when the oxide content exceeds four monolayers. XPS measurements confirm the dispersion of MOX species (M = V, Mo) on the surface of the support in the monolayer region; they also show that disordered and paracrystalline oxide phases occupy a limited area of the monolayer surface, but could not distinguish between them. ESR results showed 95% of the supported vanadium in the oxidation state +5. Phosphorus and potassium impurities in (or on) the TiO2 support influence the structure and catalytic properties of the VOX monolayer phase. In the case of catalysts made on supports with low impurities, activities in butadiene oxidation and isopropanol decomposition are principally due to the monolayer species and little contribution is made by the disordered or paracrystalli ne V205, while in the catalysts made on the supports with relatively high level of impurities, the activities in both reactions increase with V205 content in the region of one to four monolayers. MoOX catalysts showed low activities and selectivities in butadiene oxidation.

No description available.

published_or_final_version / Chemistry / Master / Master of Philosophy