The Cutler-Hammer plant in Bowling Green, Kentucky,manufactures laminated steel armatures for electrical starters (large relays) on which corrosion occurs only in some regions. The manufacturing process includes a heat treatment step from which the laminations emerge with a non-uniform surface appearance. Laminations from corroded regions of an armature have red oxide (Fe203) on the edges, while the sides have a black coating of partly-burned cutting-machine oil residue. The purpose of the project was to investigate the mechanisms of this corrosion and why it does not occur uniformly and to suggest practical solutions for the plant. Emission spectroscopy revealed no great differences in the content of minor constituents, although some elements (Li and Mg) were present in traces only in the surface of corroded samples. X-ray crystallography indicated that the surface of uncorroded strips has a more complex structure than that of corroded strips. Both samples showed diffraction lines that agreed with standard values for body-centered cubic iron. For the uncorroded sample, X-ray diffraction also showed protective Fe3C, Si02' and other unidentified compounds coating the surface. In dilute acid the black coating soaked loose from corroded regions and corrosion occurred uniformly over the side surfaces. Uncorroded laminations were somewhat more resistant. In controlled heat treatment experiments oxygen in the oven atmosphere carried out direct chemical attack on unprocessed lamination surfaces to form iron oxides. Formation of red oxide (Fe203) was at a maximum for 900°F, 60 minutes. At 1100°F, 60 minutes, the laminations tended to form black oxide (Fe304) which is more resistant to further corrosion. These results suggest that the direct attack of oxygen may begin during the heat treatment in the manufacturing process. If an ovencorroded lamination is riveted beside an uncorroded lamination in an armature, a cell may be set up and further corrosion may occur electrochemically. As possible remedies, the plant may use lower temperature and longer time, use a reducing atmosphere oven, or replace the heat treatment with a solvent process.

By optimizing parameters including temperature, reaction time, reagent concentration and pressure, the optimum conditions for the mild oxydesulfurization of coals were determined to be 150°C-200"C and 10 atmospheres oxygen in aqueous slurries of coal reacted with 1 M NH4OH for 1.5-2 hours. The total amount of sulfur removed from -60 mesh coals ranges from 51% to 78% with a mean of 64%, while the amount of inorganic sulfur removed from the coals ranged from 66% to 91% with a mean of 77%. The amount of organic sulfur removed from the samples ranged from 36% to 50% with a mean of 43%. Thermal analysis of raw and cleaned coals was carried out. By using a heated gas line to connect the thermal gravimetric analysis to the Fourier transform infrared instrument (TG/FTIR), the main products from the combustion of raw and cleaned coals were found to be CO2, H20, and SO2. The IR spectral data for SO2 were collected at 1375 cm' throughout the combustion process for raw and cleaned coals. The temperatures for aliphatic, pyritic and aromatic sulfur oxidation were determined to be 320°C, 420°C, and 470°C, respectively. Based on the thermal analysis experiments, an instrumental analysis method for the determination of pyritic sulfur was designed. The amount of pyritic sulfur determined the TG/FTIR method compared favorably to data obtained using the ASTM D 2492 method. X-ray absorption fine structure (XAFS) spectra of selected samples were obtained by Dr. Frank Huggins at the University of Kentucky. These spectra supported the results obtained in the oxydesulfurization and TG/FTIR experiments.

French chemists found that the reaction of trifluoroacetic anhydride with the N-oxide of trimethlyamine leads to the methylenedimethylimmonium trifluoroacetate. This salt is considered to be the actual reagent in the Mannich reaction conducted with dimethylamine and formaldehyde. Indeed use of this salt gives higher yields than those obtained via the classical Mannich procedure. This salt could be distilled under vacuum (5 x 10-2 mm) and reacted with phenylmagnesium bromide to give an 80% yield of benzyldimethylamine. The trimethlsilyl ethers of ketones were employed as intermediates and exhibited regioselectively. For unsymmetrical ketones, the more stable enol was formed thermodynamically and the less hindered enolate was produced kinetically. The silyl ether isomers were followed by quenching with immonium salt and resulted in the regiospecific products of Mannich base. For α, β-unsaturated ketones, the enolate was formed in high yield by 1,4-addition when lithium dimethylcuprate was employed. ϒ-Butyrolactone could be alkylated, providing an intermediate to the construction of an α-methylene lactone, a moiety present in several compound having appreciable anti-tumor activity.

The synthesis and characterization of some new metallocenes is discussed. These organometallic compounds contain some of the first reported pi-complexes between an aromatic ylid, triphenylphosphoniumcyclopentadienvlide. and some transition metals. Also reported is the synthesis of some new mercury halide metallocenes involving dimethylsulfoniumcyclopentadienylide as the sigma bonded organic substrate.

Bituminous coals were desulfurized by leaching in a 325 ml, agitated, autoclave with hot, dilute solutions of carboxylic acids, buffered carboxylic acids, carboxylic salts, and carboxylic salt:alkali combinations. The partial pressure of oxygen was not increased as it was found not to increase the amount of organic sulfur removal. The effect of increasing carboxylic size and decree of desulfurization was studied. Among the carboxylic acids studied, formic acid removed the greatest amount of organic sulfur;and iso-valeric acid removed the greatest percentage of pyritic sulfur. It was found that there is a direct correlation between the amount of organic sulfur removal and the ASTM determined volatile matter of the coals.

Given the proper equations and the appropriate set of selection rules, a computer can be programmed to simulate the spectrum of a molecule. This study deals with the rotational spectrum of a symmetric top molecule. The program itself was written in several subroutine blocks. By doing this the computing time was reduced by 70% over similar programs. The program can be used to simulate the spectrum of a molecule if the transition polarization type and the rotational constants are known. However, if the type of transition polarization or constants is unknown, the program can be used as a tool for data determination.

High Density Polyethylene (HDPE) is a highly flammable compound. Finding a method to reduce HDPE's flammability is of great scientific interest to researchers and industry. Chlorination of the HDPE has been shown to have an effect on the flammability of the polymer. This study looks at the effects of various chlorinated samples on the thermal decomposition of HDPE in atmospheres of nitrogen, air, and oxygen. The thermal analysis instruments used were a Thermogravimetric Analyzer (TGA), and a Differential Scanning Calorimeter (DSC). To study the gaseous products evolved during thermal decomposition of the polymer Fourier Transform Infrared Spectrophotometry (FTIR) and Gas Chromatography (GC) data were obtained. The results obtained showed that increasing chlorination suppresses the decomposition rate of the polymer by decreasing the flammability.

Plasticity is a phenomenon of certain coals that is not completely understood. Some bituminous coals go through a softening and swelling state upon heating before they re-solidify. It is this softening and swelling state that is labeled as the "plastic state" of the coal. Concurrent with the plastic state of the coal, thermal decomposition of the coal takes place. Several low molecular weight gases are also evolved. These occur at a temperature of approximately 450° C. The plasticity of a coal is a good indication of the coking ability of a coal. Plastic coals tend to give higher yields in liquefaction reactions than do nonplastic coals, a fact very useful to the synfuel industry. Fluidized bed reactors are impaired by the use of plastic coals, as they tend to agglomerate in the bed. Currently the ASTM approved method used to determine plasticity is by using a Gieseler plastometer. Gieselers are inconsistent and an easier, more efficient method is needed. It Is currently thought that the bitumen in the coal, the extractable portion of the coal, is responsible for Initiating the plasticity mechanism. It is logical, then, to assume that the amount of bitumen in the coal could be used as a predictor or the degree of plasticity. Dimethylformamide (DMF) was used as the solvent for the Soxhlet extraction of 43 highly characterized bituminous coals. A correlation between the DMF extraction data and the coal plasticities shows that DMF extraction is a reasonable technique to use to predict plasticity.

2-(2-nitropropenyl)thionhene, 2-(2-nitropropenyl) pyrrole, and 2-(2-nitropropenyl) furan were prepared and irradiated in undenatured 95% ethanol and 2% aqueous acetone. The pyrrole derivative was found to undergo a slow photodecomposition to tars. The thiophene derivative produced 60% of an α-oximino ketone and 30% of an oxazine cyclization product when irradiated In ethanol. When irradiated in acetone 47% of the oxime was produced in addition to 7% of the oxazlne. The furan derivative produced 12% of an α-oximino ketone and 51% of an oxazine cyclization product when irradiated in ethanol. When irradiated in acetone 15% of the oxime and 32% of the oxazine were produced. The decrease in yields of the oximes, as compared to the near quanitative yields obtained from the irradiation of β-methyl-β-nitrostyrene, is believed to be due to the lowered resonance energy of these heteroaromatic systems. Kinetic studies showed that more than one mechanism is in operation. Solvent studies showed that acetone plays a definite role in promoting the nitro-nitrite rearrangement.

The common bacterial genera Pseudomonas and Acinetobacter are ubiquitous in most soils and are capable of degrading a large number of chemical compounds. While the degradative pathways of several individual aromatic compounds are known, the degradative pathways of many other aromatic compounds have not yet been elucidated. In addition, very little work has been done on the microbial degradation of coal liquids in the environment. Previous work at Western Kentucky University has shown that decomposition of Ashland Oil Company's liquified coal can indeed be accomplished by the above bacterial genera in an enriched liquid media. The topic of this thesis is the decomposition of H-coal liquid and several selected aromatic compounds by soil containing viable microorganisms.