Thesis (M.A.)--Humboldt State University, 2006. / Includes bibliographical references (leaves 57-62). Also available via Humboldt Digital Scholar.

Thesis--University of Missouri, School of Mines and Metallurgy, 1910. / The entire thesis text is included in file. Typescript. Illustrated by author. Title from title screen of thesis/dissertation PDF file (viewed March 5, 2009)

Resumo: Vidros e vitrocerâmicas foram obtidos dos sistemas oxifluoretos envolvendo os fluoretos de chumbo e cádmio e um óxido conhecido como formador de vidros: SiO2, B2O3, P2O5, e TeO2. Os domínios vítreos foram estabelecidos e um grande número de composições incluindo alta concentração de metais pesados leva à formação de vidros estáveis. A estrutura amorfa foi estudada por técnicas espectroscópicas de determinação de estruturas a curtas distânicas (Espalhamento Raman e Absorção de Raios X). Além dos óxidos, o papel de formador desempenhado pelos átomos de cádmio foi também identificado. Atenção especial foi direcionada aos processos de cristalização. Fluoreto de chumbo cúbico β-PbF2, telurito de chumbo PbTe3O7 (fase cristalina de uma vitrocerâmica transparente), óxido de telúrio tetragonal α-TeO2 e soluções sólidas do tipo Pb1-xCdxF2 foram obtidos como produtos da cristalização, dependendo da composição e do tratamento térmico. A adição de íons terras-raras leva ao controle do processo de cristalização. Na presença do íon nucleante apenas a forma β-PbF2 foi identificada. Os íons terras raras apresentamse concentrados na fase cristalina e as propriedades espectroscópicas são aquelas apresentadas em um meio cristalino, sugerindo interessantes aplicações destes materiais na indústria tecnológica. / Abstract: Glasses and glass-ceramics have been obtained in oxyfluoride systems involving lead and cadmium fluorides and one of the well-known glass former oxides SiO2, B2O3, P2O5, GeO2 and TeO2. Vitreous domain were established and a wide range of compositions including high heavy metal contents lead to stable glasses. Amorphous structures have been studied by short-range order spectroscopy techniques (Raman scattering and x-ray absorption) and molecular basic structures have been identified. Besides the usual oxides, the role of glass former could also be proposed for cadmium ions. Special attention has been paid for crystallization process. Cubic lead fluoride, cubic lead tellurite, tetragonal tellurium oxide and a solid solution of the type Pb1-xCdxF2 are obtained as crystallization products depending on the composition and temperature of heat treatments. Pb1-xCdxF2 solid solutions are well known superionic materials and obtaining this solid solution as a crystal phase could be very interesting for applications concerning ionic electrical conduction properties. The addition of rare earth ions led to the control of the crystallization process. In the presence of the nucleating ion only the cubic form β-PbF2 was identified. Rare earth ions are concentrate in the crystal phase and crystal like spectroscopic properties were observed suggesting interesting applications for these perfectly transparent glass ceramics in photonics. / Orientador: Sidney José Lima Ribeiro / Coorientador: Younès Messaddeq / Banca: Valérie Briois / Banca: Marcel Poulain / Banca: Valmor Roberto Mastelaro / Banca: Aline Yvete Ramos / Doutor

SWISS STEEL, filiale du groupe SCHMOLZ + BICKENBACH, finance des travaux de thèse menés au Centre de Recherches d’UGITECH, en collaboration avec le laboratoire SIMaP de Grenoble. Le but de ce programme est de trouver des alternatives au plomb (Pb) dans les aciers bas carbone de décolletage. Les objectifs sont de conserver le niveau d’usinabilité des aciers de décolletage au plomb, sans leurs défauts (toxicité, recyclage des aciers au plomb). La production d’acier au plomb est stratégique pour SWISS STEEL, puisqu’elle représente environ 30% de son activité. Parmi les différentes alternatives signalées dans la littérature, l’addition d’étain, et la graphitisation des aciers, sont les concepts les plus intéressants. En effet, il est suggéré que l’étain présente un comportement similaire à celui du plomb lors de l’usinage. Par ailleurs, Le graphite est connu pour être un lubrifiant utilisé dans des applications industrielles, ce qui peut améliorer l’usinabilité. Une caractérisation complète d’aciers industriels au plomb, et sans plomb, en provenance de SWISS STEEL (11SMn30 et 11SMnPb30), a été menée : analyse chimique, observations métallographiques et microscopiques (MEB), propriétés mécaniques, etc. Ensuite, nous avons essayé de comprendre les mécanismes par lesquels le plomb améliore l’usinabilité des aciers de décolletage aux basses vitesses de coupes (Vc < 100 m/min), grâce à des essais d’usinage spécifiques. Des calculs thermodynamiques ont été menés sur le procédé de graphitisation, et des analyses d’aciers ont été déterminées. Ce qui nous a conduits à élaborer des aciers à l’étain et des aciers graphitiques à l’échelle du laboratoire. La caractérisation de ces coulées de laboratoire, avec la même procédure que celle utilisée par les aciers industriels, a permis de vérifier la fiabilité de ces concepts, et leur bienfaits sur l’usinabilité. Des résultats encourageants ont été enregistrés. Pour une étude plus approfondie, il a été proposé de produire, à l’échelle industrielle, une analyse d’acier particulière, susceptible de remplacer le plomb dans les aciers de décolletage au plomb. / SWISS STEEL, a steel company part of SCHMOLZ + BICKENBACH group, has supported a PhD program, lead in UGITECH’s Research Center, in collaboration with the SIMaP laboratory of Grenoble. The aim of this program is to find some alternatives to lead (Pb) in low carbon free-cutting steels. The objectives are to keep the machinability level of leaded free-cutting grades without their drawbacks (toxicity, recycling of Pb steels). The production of leaded free-cutting steels is strategic for SWISS STEEL, since it represents about 30% of its activity. Among the different alternatives pointed out by the bibliography, tin addition, and graphitisation of steels, were the most interesting concepts. Indeed, it is suggested that tin presents a similar behaviour to that of lead during machining. Moreover, graphite is a well known lubricant in industrial applications, which could improve machinability. A complete characterisation on leaded, and non-leaded, grades form SWISS STEEL has been carried out (11SMn30 and 11SMnPb30): chemical analysis, metallographic and SEM observations, mechanical properties, etc. Then we tried to understand, thanks to specific machining tests, the mechanisms by which lead improves the machinability of free-cutting steel, at low cutting speed (Vc < 100 m/min). Thermodynamic calculations have been performed to study the graphitisation process, and conducted to the determination of steels analyses. This lead us to develop tin-added-, and graphitic steels at the laboratory scale. The characterisation of these laboratory grades, with the same procedure, than that of industrial steels, allowed to check the reliability of these concepts, and their benefits on machinability. Promising results have been recorded. For deeper exploration, it has been proposed to produce, at the industrial scale, a particular steel analysis, which could replace leaded free-cutting steels.

The literature relating to the ontogeny of the opioid system and to the toxic effects of lead in both man and animals with particular reference to neurochemical and behavioural toxicity of lead is reviewed. The effects of perinatal lead exposure on the development of several aspects of opioid function has been studied using a dosing model of lead (as the acetate) in the maternal drinking water from conception until postnatal day 14 or 21. This model of low level perinatal lead exposure in rats had no toxic effects on growth and produced blood lead levels close to the safety limits set for human exposure and similar to those that have been recorded in some children. The ontogeny of morphine antinociception using the tail immersion test and ketocyclazocine in the paw pressure test was studied in 10,21 and 30 day old rats. Perinatal lead exposure decreased the antinociceptive activity of both morphine and ketocyclazocine in 10 day old rats. Recovery of morphine antinociception occured by 21 days and ketocyclazocine antinociception by 30 days. Radioligand binding studies with [3H]DAGO were used to study the ontogeny of u-opioid receptors in 10,21 and 30 day old rats. Perinatal lead exposure was without effect on equilibrium dissociation constant or maximal binding capacity. Radioligand binding studies with [[3]H] DPDPE were used to study the ontogeny of 6 -opioid receptors in rats between 15 and 50 days. The affinity of the 6-opioid binding site for [[3]H] DPDPE was reduced by perinatal lead exposure but without accompanying changes in binding capacity. This effect of lead on s-opioid receptors was persistant and was observed in rats aged 15-50 days. Basal plasma corticosterone levels (measured fluorimetrically) were elevated by perinatal lead exposure in 45 and 60 day old rats but not in 30 day old rats. In addition the modulatory effect of morphine on stress induced elevations of corticosterone levels was also affected by lead exposure. A reduced effect of morphine was seen in 30 day old animals whilst an increased effect was seen in 60 day old animals. Locomotor activity (measured by photocell detection) of 10,21 and 30 day old rats was recorded over 1 hour during the dark phase of the light/dark cycle. Exploratory locomotor activity was reduced in lead exposed animals at postnatal day 10 and the hypolocomotor effect of morphine was also increased in 10 day old lead exposed animals. The opioid system is particularly sensitive to perinatal low level lead exposure and this is manifested in several aspects of physiological function. Possible mechanisms by which lead affects the development of the opioid system are discussed.

Orientador: Carmen Maria Bueno Neme / Banca: Maria de Lourdes Merighi Tabaquim / Banca: Olga Maria Piazentin Rolim Rodrigues / Resumo: O chumbo, utilizado em larga escala em processos industriais, é um dos principais poluentes ambientais do planeta. Os efeitos de sua exposição vem ser tornando problema de saúde pública, com descobertas sobre danos cognitivos em níveis de contaminação cada vez mais baixos. Em Bauru, em 2002, uma fábrica de baterias automotivas provocou um acidente ambiental em que foram contaminadas 314 crianças de zero a 12 anos de idade, o que uniu profissionais de diversos segmentos para diagnósticos e tratamentos multiprofissionais específicos. O setor de psicologia da Universidade Estadual Paulista (UNESP) formou um grupo de pesquisa, cujo projeto inicial denominado "Atendimento emergencial à crianças de zero a 12 anos de idade contaminadas por chumbo", vem gerando sub-projetos e pesquisas, dentre as quais a presente. Trata-se de um estudo longitudinal, que compara quantitativa, qualitativa e estatisticamente, resultados de avaliação intelectual de crianças contaminadas por chumbo, com plumbemia entre 15.40'mü'g/dl e 30'mü'g/dl na avaliação e entre 10.30'mü'g/dl a 21.90'mü'g/dl, na reavaliação. O instrumento utilizado foi o WISC-III, adaptado e padronizado para a população brasileira. Foram reavaliados 10 participantes de ambos os sexos, com idades entre 7a 5 m a 9a 9m na avaliação e 11a 8m a 13a 8m na reavaliação; com escolaridade entre 1ª e 3ª série na avaliação e 5ª e 7ª série na reavaliação, cujo critério de seleção era ter sido avaliado... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Lead, which is broadly used in industrial processes, is one of the main environmental pollutants of the planet. The effects of being exposed to lead, is becoming a public health problem, considering that it was found some cognitive damage even in levels of contamination relatively low. In Bauru, in 2002, an automotive battery plant caused an environmental accident in which 314 children, from 0 to 12 years of age were contaminated. This fact reunited professionals of several areas for specific treatment. The psychology department of São Paulo State University (UNESP), formed a research team denominted "Emergy attendance for children from 0 to 12 years, contaminated by lead", which has been arising sub-projects and researches, including the present one. This is a longitudinal study, which compares quantitative, qualitative and statistical outcomes of the intellectual assessment of Bpb children, ranging from 15.40'mü'g/dl and 30'mü'g/dl on the evaluation and ranging from 10.30'mü'g/dl to 21.90'mü'g/dl on the reevaluation. The instrument applied was WISC-III, which was adapted and standardized for the Brazilian people. Ten subjects from both sexes were evaluated; their ages ranged from 7 years and 5 months to 9 years and 9 months; when they were revaluated their ages ranged from 11 years and months to 13 years and 8 months. During the evaluation period these children were attending from first to third grades and on the reevaluation they were attending from 5th to 7th grades, in which the selection criteria was the assessment applying WISC - III in 2002 remaining with... (Complete abstract click electronic access below) / Mestre

Accurate sediment flux histories are critical data for deciphering the relative importance of climate and land use factors such as logging and road construction on sediment production and deposition. We use 210Pb activities derived from sediment cores taken on the tidal flats of the South Slough of the Coos Bay estuary to establish temporal variations in sediment accumulation rates. We determined that average deposition varied between 0.4 and 0.81 cm/yr based on two ~80 cm sediment cores. Sedimentation accumulation rates approached 2.1 cm/yr during the 1960s when a rainfall event of extreme intensity coincided with vigorous timber activity. Following this peak, a >40% reduction in peak lumber harvests in the latter part of the 20th century was accompanied by a decrease in sedimentation rates. Mean monthly rainfall during the same time period remained seasonably constant, indicating that land use is likely the key factor governing variations in sediment accumulation.

This work hereby presents the synthesis, spectroscopic and photophysical properties of newly synthesized lead (PbPc) and antimony (SbPc) phthalocyanines. The complexes are either unsubstituted or substituted at the peripheral and non-peripheral positions with phenoxy, 4-t-butylphenoxy and 4-benzyloxyphenoxy groups. The photophysical properties of these complexes were studied in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform as solvents. The fluorescence spectra for PbPc complexes were different to that of the excitation spectra due to demetallation upon excitation. On the other hand, the excitation spectra of oxidized antimony (Sb(V)Pc) derivatives were found to be similar to absorption spectra. High triplet quantum yields for PbPc and SbPc complexes ranging from 0.70 to 0.86, low triplet lifetimes (20–60 μs in DMSO, while they were <10 μs in the rest of the solvents) and low fluorescence quantum yields were observed and is attributed to the presence of heavy atoms (Pb and Sb ions). The nonlinear optical properties of PbPc complexes were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.8 W/cm2. The photodegradation studies of the PbPc and SbPc complexes synthesized showed that then are stable.

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