Uma variedade específica de quartzo de cor verde, seja natural ou induzida pela radiação é muito rara. Trata-se de um mecanismo de formação de cor completamente diferente daqueles conhecidos e amplamente discutidos na literatura, que são responsáveis pela formação do quartzo fumê, do citrino e da ametista, incluindo a prasiolita produzida pelo aquecimento da ametista de Montezuma (MG). Somente duas ocorrências, conhecidas até o momento, tem o quartzo incolor, uma no pequeno distrito em Thunder Bay Amethist Mine, no Canadá e a outra na Bacia do Paraná ( Brasil) , ao longo de uma faixa de 600 km, com ocorrências dispersas de geodos, que se estende da região de Quaraí (RS) até a localidade de Uberlândia (MG). Estas duas ocorrências foram formadas sob fortes atividades hidrotermais, a de Thunder Bay é devido ao tectonismo e a da Bacia do Paraná está relacionada às atividades da água meteórica e hidrotermal do Aquífero Guarani. Estes cristais de quartzo hidrotermal apresentam um histórico de crescimento muito rápido, permitindo a formação dos defeitos de crescimento como as geminações, o crescimento em mosaico, as formações com pequenos ângulos inclinados e as estrias que facilitam a absorção da água na forma de água molecular, silanol (Si-OH), hidroxila (OH) e como micro inclusões. Este tipo de quartzo pode ser considerado como quartzo hidratado (wet quartz) semelhante ao quartzo sintético. O teor em água, com até 3200 ppm em massa, é superior à concentração das impurezas estruturais como o Fe, Al e Li. Não existe uma correlação entre o conteúdo da água e a quantidade de impurezas, como ocorre em outras variedades de cor do quartzo. No quartzo hidrotermal de geodos são formados complexos de silanol que quando são irradiados geram os centros de cor NBOHC (Centro de cor do oxigênio com elétron desemparelhado que não participa da ligação) que apresenta absorção no intervalo de 590 nm a 620 nm e formando uma janela de transmissão a 550 nm aproximadamente, responsável pela cor verde. Várias técnicas de análises químicas e de espectroscopia foram empregadas para caracterizar estas amostras de quartzo verde. A determinação do teor de água por meio dos espectros de infravermelho FTIR mostraram menos água (até 2300 ppm em massa), em comparação com os resultados das análises de aquecimento (3200 ppm) decorrente provavelmente, ao complexo silanol remanescente. Para documentar a influência da água na formação da cor verde foram realizadas análises por espectroscopia de infravermelho FTIR em amostras de quartzo de 3 diferentes grupos de ambientes geológicos, o quartzo pegmatítico com Al e Li formado à alta temperatura da região de Santana do Araguaia, o quartzo de veios hidrotermais com Al, mas sem água originado à média temperatura, da região de Curvelo e a ametista com muito Fe, pouco Al e pouco silanol da região de Brejinho e o quartzo de geodos hidrotermais formado a baixa temperatura com alto conteúdo de água molecular e silanol, e com muito Fe e pouco Al. As análises e as comparações permitiram diferenciar e determinar a formação do centro de cor NBOHC (Centro de cor do oxigênio com elétrons desemparelhados que não participam da ligação) para o quartzo hidrotermal de geodos da Bacia do Paraná. Assim, somente cristais de quartzo com alta concentração de água molecular e silanol são apropriados para desenvolver a cor verde por meio da radiação gama. Pode-se mencionar que no mesmo geodo podem coexistir cristais de quartzo com diferentes teores de água. Cabe ressaltar também que o quartzo verde tratado com radiação gama é sensível à radiação ultravioleta e ao aquecimento, levando à perda parcial ou total da cor verde. / A specific variety of quartz showing a green color in nature or induced artificially by radiation is quite rare. This can be explained by the fact that the mechanism of formation of this color is very different from the ones widely discussed in the literature and responsible for the formation of the fumée, citrine and amethyst types of quartz, including the prasiolite (leak green quartz) formed by heating amethyst from Montezuma, Brazil. Only two occurrences are known today, where this type of quartz can be found: Canada, at the Thunder Bay Amethyst Mine, Ontario, a small district, and Brazil, at widely scattered geode occurrences along a 600 km stretch from Quaraí at Brazils southernmost tip to Uberlandia in Minas Gerais. These two occurrences have been formed by strong hydrothermal activities, at Thunder Bay due to tectonics and in Brazil by meteoric and hydrothermal waters of the Guarani aquifer. That way much quartz crystals showed a very fast growth history facilitating the formation of growth defects (twinning, small angle tilting, mosaic growth, striations) and the uptake of water in form of micro inclusions, molecular water, silanol (Si-OH) and OH. This type of quartz can be considered ¨wet quartz¨, similar to synthetic quartz. The water content with up to 3200 ppm by weight exceeds the amount of charge balancing cations (Fe, Al, Li). There is no correlation between water content and cations as in other color varieties. Instead, silanol complexes are formed, which by radiation due to gamma rays form the color center NBOHC (non-bonding oxygen hole defect), showing absorption between 590 to 620 nm and leaving a transmission window at about 550nm, responsible for the green color. To characterize samples which will be colored green by gamma rays analyses by ICP, NAA, Electron microscopy, water loss techniques and UV-VIS and NIR-FTIR spectroscopic have been made. The spectroscopic water determination showed less water (up to 2300 ppm by weight) compared with heating techniques (3200 ppm), probably due to remaining silanol complexes.To trace the influence of water on color formation, samples from 3 different geological settings (high temperature pegmatitic quartz with Al and Li, from Santana de Araguaia; intermediate temperature vein quartz with Al but without water from Curvelo; amethyst with more Fe, less Al and small silanol content from Brejinho, and low temperature regimes from geodes, high silanol and high molecular water, cations similar to the above mentioned) have been analised by NIR spectroscopy.The former will not show green color, only the latter one. It may be mentioned that even in geodes one has crystals with high and intermediate water content coexisting. The crystals with high silanol and molecular water are the ones to treat by radiation. The radiation induced color is heat and UV sensible with bleaching by longer exposure to these factors.

Uma variedade específica de quartzo de cor verde, seja natural ou induzida pela radiação é muito rara. Trata-se de um mecanismo de formação de cor completamente diferente daqueles conhecidos e amplamente discutidos na literatura, que são responsáveis pela formação do quartzo fumê, do citrino e da ametista, incluindo a prasiolita produzida pelo aquecimento da ametista de Montezuma (MG). Somente duas ocorrências, conhecidas até o momento, tem o quartzo incolor, uma no pequeno distrito em Thunder Bay Amethist Mine, no Canadá e a outra na Bacia do Paraná ( Brasil) , ao longo de uma faixa de 600 km, com ocorrências dispersas de geodos, que se estende da região de Quaraí (RS) até a localidade de Uberlândia (MG). Estas duas ocorrências foram formadas sob fortes atividades hidrotermais, a de Thunder Bay é devido ao tectonismo e a da Bacia do Paraná está relacionada às atividades da água meteórica e hidrotermal do Aquífero Guarani. Estes cristais de quartzo hidrotermal apresentam um histórico de crescimento muito rápido, permitindo a formação dos defeitos de crescimento como as geminações, o crescimento em mosaico, as formações com pequenos ângulos inclinados e as estrias que facilitam a absorção da água na forma de água molecular, silanol (Si-OH), hidroxila (OH) e como micro inclusões. Este tipo de quartzo pode ser considerado como quartzo hidratado (wet quartz) semelhante ao quartzo sintético. O teor em água, com até 3200 ppm em massa, é superior à concentração das impurezas estruturais como o Fe, Al e Li. Não existe uma correlação entre o conteúdo da água e a quantidade de impurezas, como ocorre em outras variedades de cor do quartzo. No quartzo hidrotermal de geodos são formados complexos de silanol que quando são irradiados geram os centros de cor NBOHC (Centro de cor do oxigênio com elétron desemparelhado que não participa da ligação) que apresenta absorção no intervalo de 590 nm a 620 nm e formando uma janela de transmissão a 550 nm aproximadamente, responsável pela cor verde. Várias técnicas de análises químicas e de espectroscopia foram empregadas para caracterizar estas amostras de quartzo verde. A determinação do teor de água por meio dos espectros de infravermelho FTIR mostraram menos água (até 2300 ppm em massa), em comparação com os resultados das análises de aquecimento (3200 ppm) decorrente provavelmente, ao complexo silanol remanescente. Para documentar a influência da água na formação da cor verde foram realizadas análises por espectroscopia de infravermelho FTIR em amostras de quartzo de 3 diferentes grupos de ambientes geológicos, o quartzo pegmatítico com Al e Li formado à alta temperatura da região de Santana do Araguaia, o quartzo de veios hidrotermais com Al, mas sem água originado à média temperatura, da região de Curvelo e a ametista com muito Fe, pouco Al e pouco silanol da região de Brejinho e o quartzo de geodos hidrotermais formado a baixa temperatura com alto conteúdo de água molecular e silanol, e com muito Fe e pouco Al. As análises e as comparações permitiram diferenciar e determinar a formação do centro de cor NBOHC (Centro de cor do oxigênio com elétrons desemparelhados que não participam da ligação) para o quartzo hidrotermal de geodos da Bacia do Paraná. Assim, somente cristais de quartzo com alta concentração de água molecular e silanol são apropriados para desenvolver a cor verde por meio da radiação gama. Pode-se mencionar que no mesmo geodo podem coexistir cristais de quartzo com diferentes teores de água. Cabe ressaltar também que o quartzo verde tratado com radiação gama é sensível à radiação ultravioleta e ao aquecimento, levando à perda parcial ou total da cor verde. / A specific variety of quartz showing a green color in nature or induced artificially by radiation is quite rare. This can be explained by the fact that the mechanism of formation of this color is very different from the ones widely discussed in the literature and responsible for the formation of the fumée, citrine and amethyst types of quartz, including the prasiolite (leak green quartz) formed by heating amethyst from Montezuma, Brazil. Only two occurrences are known today, where this type of quartz can be found: Canada, at the Thunder Bay Amethyst Mine, Ontario, a small district, and Brazil, at widely scattered geode occurrences along a 600 km stretch from Quaraí at Brazils southernmost tip to Uberlandia in Minas Gerais. These two occurrences have been formed by strong hydrothermal activities, at Thunder Bay due to tectonics and in Brazil by meteoric and hydrothermal waters of the Guarani aquifer. That way much quartz crystals showed a very fast growth history facilitating the formation of growth defects (twinning, small angle tilting, mosaic growth, striations) and the uptake of water in form of micro inclusions, molecular water, silanol (Si-OH) and OH. This type of quartz can be considered ¨wet quartz¨, similar to synthetic quartz. The water content with up to 3200 ppm by weight exceeds the amount of charge balancing cations (Fe, Al, Li). There is no correlation between water content and cations as in other color varieties. Instead, silanol complexes are formed, which by radiation due to gamma rays form the color center NBOHC (non-bonding oxygen hole defect), showing absorption between 590 to 620 nm and leaving a transmission window at about 550nm, responsible for the green color. To characterize samples which will be colored green by gamma rays analyses by ICP, NAA, Electron microscopy, water loss techniques and UV-VIS and NIR-FTIR spectroscopic have been made. The spectroscopic water determination showed less water (up to 2300 ppm by weight) compared with heating techniques (3200 ppm), probably due to remaining silanol complexes.To trace the influence of water on color formation, samples from 3 different geological settings (high temperature pegmatitic quartz with Al and Li, from Santana de Araguaia; intermediate temperature vein quartz with Al but without water from Curvelo; amethyst with more Fe, less Al and small silanol content from Brejinho, and low temperature regimes from geodes, high silanol and high molecular water, cations similar to the above mentioned) have been analised by NIR spectroscopy.The former will not show green color, only the latter one. It may be mentioned that even in geodes one has crystals with high and intermediate water content coexisting. The crystals with high silanol and molecular water are the ones to treat by radiation. The radiation induced color is heat and UV sensible with bleaching by longer exposure to these factors.

No description available.

Les asphaltènes et autres constituants lourds du pétrole, comme les résines et les alcanes de haut poids moléculaire, posent des défis importants dans tous les segments de la chaîne de production pétrolière. Parmi les nombreux problèmes, la déstabilisation et le dépôt des asphaltènes dans les opérations en amont ont fait perdre beaucoup de temps à la recherche et ne sont pas encore complètement compris. Une partie de la difficulté à saisir la véritable physique derrière de tels phénomènes est l'utilisation répandue des systèmes modèles et des molécules extraites, modifiant considérablement l'organisation fluide complexe des pétroles bruts, et donc en contournant les processus réels. À ce jour, deux extrêmes de la structure organisationnelle asphaltenes peuvent être dessinés, en tant que partie d'un agrégat, avec des attractions pi-pi simples et des chaînes d'alcane répulsion, contrôlant l'agrégation; et dans le cadre d'une structure macromoléculaire, avec une participation significative d'autres composants bruts. La dernière structure étant beaucoup plus difficile à modéliser, elle capture sa physique et est difficilement reproductible à l'aide de systèmes modèles. Un autre aspect important de la recherche des dépôts d'asphaltènes est la manière dont se produit la déstabilisation des asphaltènes. Lorsque l'on utilise des asphaltènes extraits dans des systèmes modèles, l'affirmation précédente n'a pratiquement aucune moyenne, car les nombreuses fractions d'asphaltènes ont été préalablement mélangées. Cependant, lorsqu'il s'agit de tout le pétrole brut, la voie de la déstabilisation est importante et est encore largement dépassée au sein de la communauté scientifique. Pour résumer les sujets exposés, il y a plutôt la non-spécificité de la majorité des techniques expérimentales utilisées sur la recherche de la déstabilisation et du dépôt des asphaltènes en relation avec les dépôts d'échelle des particules.Les techniques de spectroscopie, capables de balayer les paramètres physiques interfaciaux, sont de bons candidats pour améliorer les points exposés délétères. Dans la présente thèse, le résonateur à quartz connecté à un analyseur de réseau vectoriel présente le potentiel de révéler de nombreux aspects sur la déstabilisation et le dépôt des asphaltènes directement à partir de pétrole brut (huiles vivantes, recombinées ou mortes) et de systèmes modèles. L'équilibre du pétrole brut est perturbé par les changements de solubilité dans un processus continu ou en gradin imitant les processus de production. L'interprétation des paramètres de résonance des cristaux de quartz, de la fréquence et de la dissipation d'énergie, est effectuée de manière qualitative et, dans une certaine mesure, quantitative. L'étude innove dans le sens d'étendre l'utilisation du cristal de quartz pour interpréter le processus, non seulement en détectant les changements de phase, comme c'est le cas de la majorité des études précédentes. L'évaluation des produits chimiques de production est effectuée une fois que la méthodologie a fait l'objet d'une discussion approfondie. Le potentiel de l'analyse proposée est crédité par la microscopie à force atomique qui ouvre l'horizon pour plus de recherche et d'applications potentielles de la méthodologie. Parmi les applications possibles figure le développement de capteurs d'assurance de débit capables de détecter les changements de phase et d'évaluer les dépôts in situ. / Asphaltenes and other heavy petroleum constituents, like resins and high molecular weight alkanes, pose significant challenges in all segments from the petroleum production chain. Among the many problems, asphaltenes destabilization and deposition within upstream operations has rendered tons of research time and is still not completely understood. Part of the difficulty in capturing the real physics behind such phenomena is the widespread use of model systems and extracted molecules, greatly altering the complex fluid organization of crude oils, and thus bypassing real processes. To date two extremes of asphaltenes organizational structure can be drawn, as a part of an aggregate, with simple pi-pi attractions and alkane chains repulsion, controlling aggregation; and as a part of a macromolecular structure, with significant participation of other crude components. The last structure being way more difficult to model, and captures its physics and being poorly reproducible with the use of model systems. Another important aspect when researching asphaltene deposition is the way asphaltenes destabilization occurs. When using extracted asphaltenes in model systems, the former affirmation has virtually no mean, as the many asphaltenes fractions were beforehand mixed. However, when dealing with the whole crude oil, the path of destabilization matters and is still greatly bypassed within the scientific community. Summing up to the exposed topics, there is the rather non-specificity from the majority of experimental techniques used on the research of asphaltenes destabilization and deposition in relation to the depositing particles size scales.Spectroscopy techniques, capable of sweeping interfacial physical parameters are good candidates for improving the deleterious exposed points. In the present thesis quartz crystal resonator, connected to a vector network analyzer is used is shown to present the potential of revealing many aspects on asphaltene destabilization and deposition directly from crude oils (live, recombined or dead oils) as well as model systems. Crude oil equilibrium is disturbed by solubility changes in a continuous or step gradient mimicking production processes. The interpretation of the quartz crystal resonance parameters, frequency and energy dissipation, is performed in a qualitative and to some extend quantitative way. The study innovates in the sense of extending the use of the quartz crystal to interpret process, not only detecting phase changes, as it is the case of the majority of the former studies. The evaluation of production chemicals is undergone once the methodology is thoroughly discussed. The potential of the proposed analysis is credited by atomic force microscopy which opens the horizon for more research and potential applications of the methodology. Among the possible application is the development of flow assurance sensors capable of detecting phase changes and evaluate deposition in situ.

Orientador: Carlos Kenichi Suzuki / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-23T18:37:21Z (GMT). No. of bitstreams: 1 Guerra_ChristianoPereira_D.pdf: 3352295 bytes, checksum: efe1174275c24c1520729d7316d099fe (MD5) Previous issue date: 2013 / Resumo: A sílica vítrea é um material fundamental para a indústria de alta tecnologia devido as suas propriedades únicas. Dentre estas podemos destacar a sua alta pureza aliada ao elevado ponto de fusão e alta transmitância no ultravioleta. É um material muito usado na indústria de semicondutores e em fotônica. Para aplicações na indústria óptica e de lâmpadas especiais, é necessário que a sílica vítrea tenha alta transmitância na região do ultravioleta médio (200 nm - 300 nm) e do visível e contenha um reduzido teor de bolhas. Tarugos de sílica vítrea foram produzidas pelo método de Verneuil a partir da fusão em chama com gás GLP e O2. Foram utilizados pós de quartzo natural brasileiro de diferentes regiões com variados teores de impurezas e pós de quartzo comerciais nacionais e importados. Foi introduzida uma etapa de lixiviação ácida em um dos pós de quartzo comercial brasileiro com o objetivo de diminuir o teor de bolhas na sílica vítrea. As impurezas nos pós de quartzo foram determinadas através da técnica de ICP-MS. A transmitância óptica entre 190-3200 nm foi determinada por espectroscopia óptica. O teor de OH presente nas amostras de sílica foi determinado através da banda de absorção em 2730 nm na região do infravermelho do espectro. O teor de bolhas foi determinado através de microscopia óptica, considerando bolhas maiores que 0,01 mm. Foi avaliada a relação entre a transmitância das amostras de sílica vítrea e os teores de impurezas presentes nos pós de quartzo. Os resultados de transmitância na região do médio UV das amostras de sílica vítrea produzida com pós de quartzo feitos a partir das lascas de quartzo brasileiro foram comparados com a sílica vítrea produzida com pó de quartzo comercial importado. Os teores de bolhas foram avaliados em relação às condições de processo de fusão e temperatura de fusão do tarugo. Os resultados mostram a excelente viabilidade do quartzo brasileiro para a fabricação de sílica vítrea de elevado valor agregado / Abstract: Due to their unique thermal and optical properties, silica glasses are highly demanded for use in the high technology industry. They are widely used in the semiconductor and optics industries. For most of the applications in optical industry it is necessary to present high optical transmittance in the medium ultraviolet region (200 nm - 300 nm) and visible and low content of bubbles. Silica glass rods were produced by the Verneuil method from flame fusion with LPG and O2 gases by using Brazilian natural quartz from various regions of the country and also imported and national commercial quartz powders. An acid leaching procedure in a commercial Brazilian powder quartz was tested with the purpose of reducing the bubbles content in silica glass. The measurements of impurities concentration in the quartz powders were determined by ICP-MS technique. The optical transmittance from 190-3200 nm was determined by optical spectroscopy. The OH content was determined by the absorption band at 2730 nm in the infrared region of the spectrum. The content of bubbles larger than 0.01 mm was determined by optical microscopy. The relationship between the optical transmittance of the silica glass samples and the level of impurities in the quartz powders was evaluated. The results of the average transmittance in the UV region of the silica glass samples produced from Brazilian quartz lascas were correlated with the silica glass produced using imported commercial quartz powders. The concentration of bubbles was evaluated with respect to the process conditions of fusion and ingot melting temperature. The results show an excellent feasibility of application of Brazilian natural quartz to produce high value added silica glass / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Bulk laser-induced breakdown and self-focusing in single samples of fused quartz and NaCl were examined using picosecond optical pulses at 1.0 ym and 0.5 ym. The results of three separate but related experiments are reported. First the nonlinear index of refraction, n2, of each of the test materials is measured near the respective damage thresholds of the samples. The values of 1*2 were determined by detecting beam distortions in the far field, transmitted laser beam profile caused by the irradiance dependent index of refraction. The experimental traces were compared to theoretical beam profiles generated by a nonlinear propagation code and n2 was extracted from the resulting fits.

The electrochemical quartz crystal microbalance (EQCM) has been proven an effective mean of monitoring up to nano-scale mass changes related to electrode potential variations at its surface. The principles of operation are based on the converse piezoelectric response of quartz crystals to mass variations on the crystal surface. In this work, principles and operations of the EQCM and piezo-electrodes are discussed. A conductive oxide, ruthenium oxide (RuO2) is a promising material to be used as a diffusion barrier for metal interconnects. Characterization of copper underpotential deposition (UPD) on ruthenium and RuO2 electrodes by means of electrochemical methods and other spectroscopic methods is presented. Copper electrodeposition in platinum and ruthenium substrates is investigated at pH values higher than zero. In pH=5 solutions, the rise in local pH caused by the reduction of oxygen leads to the formation of a precipitate, characterized as posnjakite or basic copper sulfate by means of X-ray electron spectroscopy and X-ray diffraction. The mechanism of formation is studied by means of the EQCM, presenting this technique as a powerful in-situ sensing device.

<p> A microscopic study of two samples of the Gowganda Formation, both having undergone pure shear deformation at greenschist f acies metamorphism has shown: Sample A -Reduction in quartz grain size, and pressure solution shadows were evidence for strong pressure solution activity. Pre-lithification fractures provided channelways for the removal of quartz and water out of the system. Matrix quartz was not recrystallized. Sample B -Extensive local recrystallization of quartz due to pressure solution activity caused metamorphic segregation and the formation of a cleavage. Cleavage behaviour differs in the matrix from that observed in an area of contact strain, as produced by a buckled quartz vein. There is no evidence for removal of quartz from the system. </p> <p> A comparison between the two samples suggests that (a) water, in this case at least, is necessary to produce metamorphic segregation, (b) the system has to be closed to reach metamorphic segregation and (c) original features may be preserved through limited metamorphism if the rock is dried out early in its history. </p> / Thesis / Bachelor of Science (BSc)

No description available.

In this thesis, a new technique for using quartz crystal microbalance (QCM) in magnetic field was explored. This technique would take advantage of the sensitive nature of QCM to vibration changes. The idea is to perturb the QCM vibrations with magnetic materials on it by applying magnetic field. A new instrument called magnetic QCM (MQCM) was constructed to explore this technique. The thesis contains three bodies of work. The first body describes the development of the MQCM instrument and the demonstration of the technique. The resonance frequency of a QCM with conducting polymer (polyaniline) suspension in poly(ethylene glycol) was observed to increase with increasing applied DC magnetic field. The change in population of free spins through doping with HCl vapor is reflected in increased frequency-field curve magnitude. The second body of work describes the study of QCM proximity phenomenon discovered during the MQCM instrument development process. When an object approaches a vibrating QCM, the resonant frequency changes. This proximity effect is seen at the distance of 10 mm in air and becomes more pronounced as the distance decreases. This effect depends on the value of quality factor, conductivity of the object, and electrical connection of the object to the QCM electrodes. A simple modified Butterworth van-Dyke model is used to describe this effect. It must be recognized that this effect may lead to experimental artifacts in a variety of analytical QCM applications. The third body of work describes an improved version of MQCM. The complex geometry such as particle suspension were simplified to alternating stack of ferromagnetic and diamagnetic layers. When magnetic field was applied, changes in the QCM admittance magnitude and phase curves were observed. A mass-equivalent stack of continuous consecutive layers of nickel and gold was also exposed to magnetic field but no changes were observed. Butterworth-van-Dyke model attributed the effect to internal shear friction loss among other losses is modulated by the magnetic field. Quantum effect was considered. However, after examining SEM surface images, the source of acoustic response to magnetic field is more likely from interfacial stresses.