Thesis (Ph. D.)--University of Nebraska, 1925. / Bibliography: p. 27-28.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1958. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 136-139).

A corrosão localizada em aços inoxidáveis pode se manifestar de várias formas, tais como, a corrosão por pite, em fresta e corrosão sob tensão. Estes tipos de corrosão ocorrem quando o metal é exposto em meios agressivos como o cloreto, entre outros. O objetivo deste trabalho é estudar o comportamento dos aços inoxidáveis austeníticos e ferríticos em meios agressivos de cloreto, brometo e suas misturas. Para testar a resistência à corrosão por pite foi usado o método de polarização potenciodinâmica em eletrólitos de concentração iônica total de 0,6M. Os materiais estudados foram os aços inoxidáveis: 298 (aço inoxidável Cr-Mn, especificação da ArcelorMittal Inox Brasil) e os aços padronizados segundo a UNS: S30400, S31603, S43000 e S44400; todos, na condição tal como recebida da usina. Os resultados mostraram que, em meio de 0,6M(NaCl+NaBr), para concentrações de 0M a 0,45M NaCl, o desempenho quanto a resistência à corrosão por pite obedece a seguinte ordem decrescente: 444, 316L, 304, 298 e 430. Por sua vez, para a concentração de 0,6M NaCl, ou seja, ausência total de brometo, ocorre a alteração do desempenho dos aços inoxidáveis, colocando a seqüência da seguinte ordem: 316L, 444, 304, 298 e 430. Nota-se, portanto, que o melhor aço para ambientes contendo íon brometo seria o aço 444, já para aplicações em meio de cloreto puro, a melhor seleção é o aço 316L. Foram encontrados sítios de nucleação nos diferentes aços testados nos eletrólitos de 0,6M NaCl e 0,6M NaBr,sempre relacionados a inclusões: em alguns casos a nucleação ocorreu na interface matriz/inclusões insolúveis e, em outros, foram encontrados sinais de dissolução de inclusões, provavelmente de sulfeto. As diferenças de resistência à corrosão por pite entre os diferentes aços, nos diferentes eletrólitos, foram discutidas em função das diferenças de composição química. / Localized corrosion of stainless steels can be manifested in various forms, such as: pitting, crevice and stress corrosion. These types of corrosion occur due to exposition of metal in aggressive environments such as: chloride and bromide. The mean goal of this work is to study the pitting corrosion resistance of both austenitic and ferritic stainless steels in aggressive environments containing chloride, bromide or their mixtures. The potentiodynamic polarization method was used to test the pitting corrosion resistance in media containing a total of ion concentration of 0,6M. The studied materials in this work were stainless steel: 298 (Cr-Mn steel, specification of ArcelorMittal Inox Brazil) and standardized steels according to the UNS: S30400, S31603, S43000 and S44400. The results have shown that maintaining a constant concentration of 0.6M (NaCl+NaBr) into the electrolyte by varying the NaCl concentration between 0M and 0.45M, the performance in terms of pitting corrosion obeys to the following decreasing order: 444, 316L, 304, 298 and finally 430. In turn, for a concentration of 0.6M NaCl, so without any bromide, there is a variation from the performance of stainless steels, putting the sequence as following: 316L, 444, 304, 298 and 430. Nucleation sites were always found related to non-metallic inclusions in all tested stainless steels for the electrolytes of 0,6M NaCl or 0,6M NaBr. Sometimes, pits nucleation occurred at the matrix/inclusion interface, but others times, pits nucleated in water soluble inclusions. Difference of the pitting corrosion resistance between tested steel in the different electrolytes have been discussed as a function of the chemical composition.

Bromide and nitrogen are wastewater effluent constituents that have raised concern for their potential to affect disinfection byproduct (DBP) formation at drinking water treatment plants (DWTPs) downstream of wastewater discharges. Despite the toxicity of brominated and nitrogenous DBPs, wastewater treatment does not usually remove bromide and nitrogen prior to discharge. Bromide is a conservative chemical and thus is not removed from surface waters via natural transformations after being released, although it may be diluted. Nitrogen is biologically reactive; it can be transformed and removed by bacteria in the environment and in wastewater treatment plants (WWTPs). While this nitrogen cycling may reduce impacts on downstream DWTPs, it also produces nitrous oxide (N2O), a greenhouse gas, as a byproduct. Thus, interaction with the environment alters the potential impact of bromide and nitrogen on drinking water systems. The objective of this work was to examine the impacts of nitrogen and bromide present in wastewater effluent on DBP formation at downstream DWTPs, within the context of current and possible future DBP regulations. Three major conclusions were reached. First, within Southwestern Pennsylvania, an area where surface water bromide concentrations have increased due to fossil fuel extraction-based wastewater discharge, no statistically significant improvement in species-specific risk was observed over the past 20 years, despite decreasing TTHM levels. Second, nitrogen treatment decisions at WWTPs influence the formation of N-nitrosodimethylamine (NDMA), an unregulated but toxic DBP, at downstream DWTPs in areas of high de facto reuse (DFR). More plants using nitrifying wastewater treatment resulted in significantly lower NDMA detection rates and concentrations observed at chloraminating DWTPs located downstream. Third, the current approach to estimating national emissions of N2O related to wastewater treatment may underestimate emissions by an order of magnitude. Further, nitrogen removal at wastewater treatment plants reduces total N2O emissions attributable to wastewater treatment by reducing the N2O that would be generated in receiving surface waters. Thus, in both cases, impacts of WWTPs on downstream DWTP DBPs were observable. While natural cycling may remove nitrogen from surface water, in-plant removal of nitrogen prevents large amounts of N2O emissions.

Lignin is a major chemical component of plants and the second most abundant natural polymer after cellulose. The concerns and interests of agriculture and industry have stimulated the study of genes governing lignin content in plants in an effort to adapt plants to human purposes. Arabidopsis thaliana provides a convenient model for the study of the genes governing lignin content because of its short growth cycle, small plant size, and small completely sequenced genome. In order to identify the genes controlling lignin content in Arabidopsis accessions using Quantitative Trait Locus (QTL) analysis, a rapid micro-scale method of lignin determination is required. The acetyl bromide method has been modified to enable the rapid micro-scale determination of lignin content in Arabidopsis. Modifications included the use of a micro-ball mill, adoption of a modified rapid method of extraction, use of an ice-bath to stabilize solutions and reduction in solution volumes. The modified method was shown to be accurate and precise with values in agreement with those determined by the conventional method. The extinction coefficient for Arabidopsis lignin, dissolved using acetyl bromide, was determined to be 23.35 g-iLcm-1. This value is independent of the Arabidopsis accession, environmental growth conditions and is insensitive to syringyl/guaiacyl ratio. The modified acetyl bromide method was shown to be well correlated with the 72% sulfuric acid method once the latter had been corrected for protein contamination and acid-soluble lignin content (R² = 0.988, P < 0.0001). As determined by the newly developed acetyl bromide method and confirmed by the sulfuric acid method, lignin content in Arabidopsis was found to be a divergent property. Lignin content in Arabidopsis was found to be weekly correlated with growth rate among Arabidopsis accessions (R² = 0.48, P = 0.011). Lignin content was also found to be correlated with plant height among Arabidopsis accessions (R² = 0.491, P < 0.0001). / Forestry, Faculty of / Graduate

The Inverse Temperature Crystallization (ITC) and seed-induced method were used to grow high-quality cubic samples within hours using a 1M solution of methylammonium lead bromide (MAPbBr3) samples. The current-voltage (I-V) hysteresis observed within the MAPbBr3 perovskite sample demonstrates anomalous dependence on scan rate and various preconditioning pulses. We investigate this dependence and the relationship of current-transient with slow migrating ions. The current transients fitted using a bi-exponential decay model produced two distinct time constants t1 = 38.4 s and t2 = 6.49 s associated with migrating ionic species. From the Arrhenius plot an activation energy of Ea = 0.410 associated with migrating Br ions was extracted. Future research is required towards the understanding of I-V hysteresis and the link to ion migration in MAPbBr3 perovskite. / Dissertation (MSc (Physics))--University of Pretoria, 2020. / NRF Funding / Physics / MSc (Physics) / Restricted

This thesis is dealing with nanowires of zinc oxide and of cesium lead bromide. Main goal was a preparation of ZnO nanowires using MBE. This goal was partially achieved and growth of needle-like structures was observed. Another goal was characterization of already prepared ZnO nanowires. We successfully determined polarity of their surfaces, examined the influence of lattice defects and assessed the result of their doping. Side goal of this work was characterization of nanostructures of cesium lead bromide. However, preparation of cesium lead bromide nanowires remains an open issue.

Randomized complete block designs with three replications were utilized to evaluate the effects of fumigation with sulfuryl fluoride (SF) (0, 12, 24, 36 and 72 mg/L), phosphine (PH3) (0, 200 and 1000 ppm at 48 hr), methyl bromide (MB) (0, 4, 8, 16, and 32 mg/L for 48 hr), carbon dioxide (CO2) (0, 60% at 48 hr and 60% at 96 hr) and ozone (O3) (0 ppm and 175 ppm for 48 hr) on the volatile flavor compound concentrations in dry cured ham. Fluoride and SF concentrations increased (P < 0.05) in dry cured hams as SF fumigation concentration increased, but all samples contained fluoride and SF concentrations below the legal limits of 20 and 0.01 ppm, respectively. Also, as phosphine fumigation concentration increased, the residual concentration of phosphine also increased in the hams (P < 0.05), but all samples contained levels that were lower than the legal limit of phosphine in stored food products (0.01 ppm). Minimal differences existed in the presence and concentration of aroma active compounds in fumigated hams when compared to the control. Triangle tests indicated that consumers could not discern (P > 0.75) between the control hams and the fumigated hams. This study revealed that there were minimal aroma/flavor differences among control hams and hams that were fumigated with SF, PH3, MB, CO2 or O3 and that fumigation of dry cured ham with SF and PH3 were safe and met legal requirements for consumption. This reveals that SF, PH3, CO2 and O3 could be tested at the industrial level to determine their efficacy as potential alternatives to methyl bromide to treat dry cured hams for insect pests.

This research investigated the influence of bromide-ion concentrations upon trihalomethane (THM) formation and speciation. There is some speculation that bromide will increase the amount of THMs on a mass and/or molar basis. Previous research had indicated that bromide will affect the speciation to form the more brominated forms of THMs, but the extent of this speciation has not been clearly defined. Speciation is important when evaluating THM removal processes. The brominated species may require activated carbon for removal as opposed to air stripping for removal of the volatile species (chloroform). To investigate the role of bromide ion, a half-fractional, factorial matrix was used in which the DOC, pH, and temperature were varied at two levels; chlorine dosage and bromide-ion concentration were varied at three levels; and time was varied at five levels (up to six days). Over 750 experimental observations were used to generate five empirical models employing the six factors. An empirical model was generated to determine the mass for the THM species and to estimate the Total THMs. The results indicate the following: 1) all variables were positively correlated to trihalomethane formation; 2) bromide-ion concentration is a significant factor for each species; 3) bromide increased the THM yield both on a mass and a molar basis; and 4) bromide shifted the species distribution almost completely suppressing chloroform production in favor of the brominated THM species.

Two organic synthetic methods for the generation of methyl bearing chiral centers have been developed using: 1) dimerization of methylketene and 2) a free radical-based addition/elimination reaction involving allyl bromides. The first method, the asymmetric dimerization of methyl ketene, followed by an asymmetric aldol reaction and the appropriate functional group manipulations enabled us to construct the (2S, 4S, 6S) trimethylnonyl subunit found in the siphonariene class of natural products. The latter method explored the stereoselective potential of a free radical-based condensation reaction by examining compounds which are known to be able to support chiral auxiliaries and chiral Lewis acids. Additionally, substituent effect on the rates of this reaction were examined closely and found to be comparable to similar, previously examined systems. The synthetic utility, magnitude and scope of this reaction are discussed. / Ph. D.