Thesis (Ph. D.)--University of Oklahoma, 1997. / Includes bibliographical references (leaves 75-78).

Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 120-132). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 120-132). Also available on the Internet.

Biomolecular imaging has become one of the most exciting potential applications of the Linear Coherent Light Source (LCLS), which is a source of intense femtosecond X-rays. It has been predicted that a highly intense pulse with pulse lengths on the order of a few femtoseconds should be sufficient to capture the image of a biomolecule before it is destroyed. However, the rate at which a large biomolecule explodes during exposure is a large unknown, and will likely be one of the major factors in determining if such imaging will succeed. Clusters were chosen as a size dependant model system, ideal to study the evolution of complex systems in X-ray fields. From earlier intense near-infrared (IR) experiments, it is known that depending on size and Z constitution, clusters explode by Coulomb or hydrodynamic forces. These two limits have very different cluster explosion times and signatures. Coulomb explosion is too fast to allow imaging, whereas a hydrodynamically expanding cluster is a much slower process. The ionization process leading to cluster explosion is strongly wavelength dependent as one passes from IR through XUV to the X-ray regime because the kinetic energy of the released electrons determines the charge imbalance within the cluster, and therefore, determines the explosion dynamics. Unlike in previous experiments performed with near IR or XUV pulses, irradiation by photons at the LCLS will lead to the ejection of energetic photo- and Auger- electrons which could easily escape from the cluster, leaving behind positive ions. The buildup of this charge during exposure can lead to a Coulomb explosion of the sample. On the other hand, if the charge accumulates, the photoelectrons will be held inside the cluster, where they could contribute to the cluster temperature and form a nanoplasma and expand hydrodynamically. The main goal of the thesis was to study the explosion dynamics of clusters generated due to their interaction with intense X-rays and look at its dependencies on the X-ray energy, photon fluence, absorption cross sections, sample constituency and sample size. This thesis also compares the results from X-rays with the corresponding results obtained using ultrashort XUV and Infrared lasers. / text

X-ray diffraction (XRD) has become one of the most powerful techniques for crystal structure studies and phase composition identifications. In this thesis, using the quantitative XRD (QXRD) technique to assist the development of reliable engineering strategies of stabilizing hazardous lead pollutants into ceramic matrix and resource recovery will be introduced. Metal stabilization strategies have been sought to replace the traditional disposal methods for the management of waste metal sludge. To demonstrate the unique capability of QXRD in monitoring the lead incorporation behavior, different ceramic precursors was used to react with lead oxide to investigating metal transformation mechanisms during the sintering process. When heating with alumina, influences of Pb/Al molar ratio, temperature, and treatment time on lead incorporation efficiency on the formation of PbAl2O4and PbAl12O19phasesweresuccessfully revealed by QXRD. Moreover, the influence of silica on lead stabilization effect was analyzed by blending amorphous SiO2 and quartz with -Al2O3 as the precursors. The results suggest that both silica precursors could crystallochemically incorporate lead into the lead feldspar (PbAl2Si2O8) structure in significant quantities. In addition, by sintering clay-based precursors with lead oxide, a complete lead incorporation into lead feldspar occurred above 950℃. Lead glass-ceramics were produced by thermally treating waterworks sludge with lead oxide, and amorphous contents in the products were quantified using QXRD. When hematite was used as a Fe-rich precursor to treat lead oxide, three types of lead ferrite crystals were observed and quantitatively determined. Furthermore, the mechanism of incorporating lead-zinc tailing with P-rich municipal waste sludge ash was investigated under different thermal conditions. By detailed X-ray diffraction analysis, Pb was crystallochemically incorporated into the Ca5.5Pb4.5(PO4)6(OH)2 crystalline structure and Zn was stabilized into Zn(Al0.5Fe1.5)O4 spinel phase. The stability of lead in all the product phases was evaluated byprolonged acid leaching, and the results indicated the lower intrinsic lead leachability of the product phases. The progress in optimizing experimental parameters in resource recovery suggest an opportunity of using QXRD technique to investigate the feasibility of extracting Pb from CRT and recycling P by struvite precipitation. A novel process of thermal reduction treatment with the addition of metallic iron (Fe(0)) to recover lead from cathode ray tube (CRT) funnel glass was introduced. The optimal operational parameters for the thermal extraction of lead from CRT glass were determined by QXRD technique as 50 wt.% Fe addition, heating at 700 °C for 30 min. Struvite crystallization for phosphorus recovery from wastewaters has gained strong attention. While the aspects of application and modeling have been widely studied, the phase composition of recovered phosphorus products was rarely reported. The obtained high degree of accuracy supports the validity of Rietveld method for the quantification of both amorphous and crystal phases in the products. QXRD results suggest the amount of increase of struvite in the products with the elevated N/P molar ratio from 0.2/1 to 1.2/1. All the results have demonstrated the capability of QXRD in contributing to the advancements of both material and environmental technologies. / published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

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No description available.

Various strategies have been tested for obtaining integrated intensities from x-ray powder diffractometer data. An asymmetric pseudo-Voigt profile function was used to fit the pattern in the region above 2θ = 35̊ (Cu-Kα radiation). At lower angles where the asymmetry was strongest and the profile function not suitable the peaks were integrated numerically. A smooth background function was estimated from the regions of minimum intensity of the pattern. The profile parameters were initially refined in small ranges of about 10̊ 2θ in order to determine their 2θ-dependence. Thereafter final refinements of peak intensities were undertaken using the profile parameters thus determined. Analysis of data from the mineral Fe-akermanite, Ca₂Mg₀. ₄Fe₀. δSi₂O₇, generated 173 integrated intensities with 1 > 2δ(1) out of 187 positions separated in 2θ by more than 0,02̊. Of the total of 213 reflections in the range, those overlapping exactly or separated by < 0,02̊ were treated as single peaks. The structure was refined using an overall isotropic temperature parameter and a parameter to compensate for preferred orientation, giving an unweighted residual of 10,4% for 14 parameters. / Thesis (M.Sc.)-University of Durban-Westville, 1988.

The base metal and platinum group metal extractive processes for two South African refineries were examined using x-ray powder diffraction. Base metal refinery matte contained nickel sulphide (Ni3S2), copper sulphide (Cu2S), nickel-copper alloy (Ni-Cu), iron oxide (Fe3O4) - nickel iron oxide (NiFe2O4) and nickel oxide (NiO). Nickel iron oxide and cobalt sulphide (CO3S4) were found in matte aeration cavities. Matte fast cooling caused alloy zoning. Alloy stoichiometry and weight percentages of matte constituents were calculated. Magnetic separation of the alloy phase was unfeasible due to high bulk and poor separation from Ni3S2. Sulphuric acid matte leaching produced residues containing copper sulphide (Cul.8S) and nickel sulphides (Ni3S4, NiS). Potassium cyanide residue leaching produced NiS-rich residues, while thiourea / hydrochloric acid leaching produced residues almost free of copper sulphide. PGM concentrates were examined. Base metals occurred as: copper sulphate pentahydrate; copper sulphate hydroxide hydrate (CU4SO4(OH)6'H2O); copper sulphide (CuS); copper platinum (Cu3Pt); nickel oxide (NiO); nickel iron oxide (NiFe2O4). Lead occurred as lead sulphate and silicon as quartz and enstatite ((Mg,Fe,Al)SiO3). Heating the concentrate to 260°C with sulphuric acid converted copper sulphide to copper sulphate. PGMs were mostly metallic. Overdrying concentrates caused pgm sintering. Drying with sulphuric acid reduced sintering. PGM oxidative leach solubility was examined. Platinum sulphide (Pt,Pd)S caused low platinum and palladium solubility. (Ru,Rh,Ir,Pt)AsS caused low rhodium and ruthenium solubility. Platinum-rhodium (Rh0.57Pt0.43), ruthenium-osmium (~Ru16Os), iridosmine (Os,Ir,Ru) also caused low pgm solubility. Silver chloride remained in residues. Concentrate overdrying produced insoluble sintered platinum, palladium monoxide, and ruthenium dioxide. In minor concentrates sintered platinum, rhodium selenide (RhSe2+x), ruthenium dioxide and possibly palladium monoxide lowered pgm solubility. Precipitates and salts were examined. Iron precipitated as iron oxide hydroxide (B-FeOOH); gold as metallic gold; lead as lead chloride. Common salts were: sodium chloride; sodium iron hydroxide sulphate hydrate (Na2Fe(SO4)2(OH)'3H2O); ammonium chloride; sodium carbonate monohydrate. PGM-Iead fusion was examined. Fusion produced the insoluble alloy Pb(Pd,Pt)3. Ruthenium dioxide reacted with lead carbonate forming lead ruthenium oxide (Pb2Ru2O6.5). Nitric acid insoluble residues also contained lead sulphate and iron oxide (Fe3O4). This study demonstrated that solution problems can be understood by identifying the crystalline insoluble phases in intractable residues. / Thesis (Ph.D.)-University of Natal, Durban, 1994.