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Os objetivos deste trabalho foram estudar, desenvolver e avaliar filmes para a captação de vapores de benzeno e amônia, tornando possível a detecção e quantificação destas substâncias no ar atmosférico, utilizando sensores piezelétricos de quartzo. Dispositivos piezelétricos destes cristais são hoje de grande importância em Química Analítica, possuindo inúmeras aplicações (meio gasoso e em solução), uma vez que se encontram muitos trabalhos no campo da eletroanalítica, enzimologia, imunoquímica, análise de alimentos, análises clínicas e em análises ambientais. O princípio do método baseia-se no fato de que o cristal de quartzo, sob um campo elétrico alternado, vibra com uma freqüência bem definida. Ao se depositar uma pequena massa de material na superfície do cristal (eletrodo), ocorre uma queda proporcional da freqüência de vibração. Depositando-se um filme (coating) que tenha afinidade pela substância que se quer detectar e quantificar, tem-se uma microbalança. À medida que o poluente passa pelo cristal ocorre a sorção do mesmo. Com o aumento da massa, a freqüência de vibração do cristal diminui proporcionalmente, sendo possível a construção de uma curva analítica, o que permite a quantificação do poluente em níveis da ordem de parte por milhão (ppm) ou mesmo parte por bilhão (ppb). No início dos estudos, várias substâncias (individualmente ou misturadas) foram investigadas como possíveis substratos captores (filmes) para detecção de benzeno e amônia. Entre elas, diferentes fases estacionárias viscosas utilizadas em cromatografia gasosa, além de alguns silicones, glicóis, ácidos orgânicos, zeólitas, complexos de metais de transição e até porfirinas. Para a detecção e quantificação de benzeno, em níveis da ordem de 10 ppm (32 mg m-3), dentre as muitas substâncias investigadas, até o presente momento, nenhuma apresentou resultados satisfatórios para a montagem de método analítico. Para a detecção e quantificação de amônia, encontrou-se que uma mistura de 50 ?L de solução de ácido glicólico em THEED (3:4 m/m) com 25 ?L de solução saturada de ácido tânico em acetona, mostrou-se a mais promissora. Nas etapas seguintes, passou-se às investigações para otimização das condições experimentais. Foram estudados, então, a melhor vazão de trabalho, os efeitos da quantidade de filme depositado sobre o cristal, efeito da temperatura, reversibilidade, entre outros. Todas as medidas foram realizadas para quatro tempos diferentes de exposição do cristal ao poluente (30 segundos, 1, 2 e 3 minutos). A quantidade de filme considerada ideal foi de 133 g, correspondendo a uma variação de freqüência de aproximadamente 67 KHz. Valores maiores, além de diminuírem a sensibilidade, geralmente causam parada das oscilações enquanto o poluente passa pelo cristal (aumento excessivo de massa), sendo que valores menores de massa provocam diminuição de sensibilidade. A melhor vazão de trabalho encontrada está na faixa de 80 a 100 mL min-1. Temperaturas entre 15ºC e 35ºC não apresentaram efeitos significativos sobre a sensibilidade do detector, ocorrendo uma diminuição da mesma em temperaturas acima deste limite. O sensor apresentou queda de freqüência linear (r = 0,999 para tempos de exposição de 30 segundos e 1 minuto, e r = 0,988 para tempos de exposição de 2 e 3 minutos) no intervalo de concentração estudado (2 à 10 ppm). Alguns possíveis interferentes foram investigados, entre eles CO, CO2, H2S, NO2 e ar atmosférico, sendo que, apenas o NO2 interferiu nas análises. Portanto, deve estar ausente do ar analisado ou deve ser retirado por algum captor específico estrategicamente inserido na linha de entrada. Estudos sobre o \"envelhecimento\"da película após preparo, mostraram que nenhum efeito considerável foi observado quanto à captação do poluente, após dois meses . Nos estudos de reversibilidade, o sensor mostrou-se irreversível, o que nos impediu de verificar o tempo de vida de uma mesma película para vários ciclos consecutivos. Contudo, este fato é compensado pela elevada sensibilidade e pelo curto tempo gasto na análise, ficando demonstrado sua grande potencialidade na detecção e quantificação de amônia no ar. / The objective of this work was to study, develop and evaluate coatings for detecting benzene and ammonia in atmospheric air, by using a piezoelectric quartz sensor. Nowadays, piezoelectric quartz sensors are very important in Analytical Chemistry due to their numerous aplications (in gaseous fase or in solution). This method is based on the fact that the quartz crystal when placed under an alternated electric field, vibrates with a well known frequency. When a very low mass of substance is deposited on the crystal surface (electrode) a proportional decrease in the vibrational frequency occurs. This coating must have affinity for the substance we wish to detect and quantify. The sorption of the pollutant occurs as it is passes through the crystal. Increased mass leads to decreased vibrational frequency in a proportional way, so it is possible to build an analytical curve and quantify the pollutant in levels of part per million (ppm) and part per billion (ppb). Many substances (individually or mixed) were investigated as possible coatings for detection of benzene and ammonia detection, such as different chromatography viscous stationary phases, glycols, some organic acids, zeolites, transition metal complexes and porphyrins. For benzene detection and quantification at the level of 10 ppm (32 mg m-3), none of the investigated substances presented satisfactory results. For ammonia detection and quantification a mixture of 50 ?L of Glycolic Acid in THEED solution (3:4 w/w) and 25 ?L of Tannic Acid in acetone solution was the most promising one. The optimization of the experimental conditions found 133 ?g as the ideal coating mass to be deposited on the crystal surface. A working flow of ix 80 to 100 mL min-1and a working temperature in the 15ºC to 35ºC range (59ºF to 95ºF) were found to be ideal. In the studied concentration range, the sensor presented linear decrease in frequency. Some possible interfering substances were investigated (CO, CO2, H2S, NO2 and atmospheric air) and only NO2 showed some interference. Although the sensor showed to be irreversible, it is also very sensitive and can therefore be used to detect and quantify ammonia.

No presente trabalho, foi montado um sistema de eletrodifusão para o estudo dos efeitos da substituição de íons alcalinos, presentes no canal estrutural, por íons de hidrogênio (H POT. +), nas propriedades termoluminescentes e ópticas do quartzo. A corrente elétrica de eletrólise apresenta, na parte inicial de aquecimento, um ombro ou pico de corrente. Através da análise do comportamento deste pico e informações obtidas de dados de absorção óptica na região espectral do infravermelho, concluiu-se que o pico presente na curva inicial de eletrólise se deve ao complexo [AL POT. 3+/M POT. +]. As medidas de termoluminescência e absorção óptica na região espectral do visível e ultra-violeta foram feitas em amostras de quartzo eletrodifundidos e não eletrodifundidos e chegou-se à proposição de uma reação envolvendo os alcalinos presentes no canal. Nesta reação, os íons alcalinos fazem o papel de centros armadilhadores de íons de oxigênio O POT. produzidos pela radiação ionizante, e estabilizadores de vacâncias de oxigênio. O aquecimento, em tomo de 300 GRAUS C, provoca a desestabilização desses centros armadilhadores, liberando os íons alcalinos que reagem com os defeitos [ALO IND. 4] POT. 0 emitindo luz TL. Aproveitando a existência de canais estruturais, semelhantes ao quartzo, tentou-se eletrodifundir H POT + no berilo. Através de medidas de termoluminescência e corrente inicial de eletrólise, discute-se a possibilidade da existência do defeito [FE POT. 3+/M POT. +] no berilo. / A system of electrodiffusion was made in the laboratory to investigate effects of exchanging alkali ions, usually present in the structural channels by protons, in the optical and thermoluminescent properties of quartz. In the initial part of heating, the sweeping current presents a peak at about 350 GRAUS C. The analysis of the behaviour of this peak with additional data of optical absorption in the region of infrared, it was concluded that the peak at 350 GRAUS C of the current is due to [AL POT. 3+/M POT. +] system. Thermoluminescence and optical absorption spectra in the visible and ultraviolet light region for swept and unswept quartz were compared. Based on this comparison it was shown that, once irradiated to gama- or X-rays, alkali ions are removed from [AL POT. 3+/ M POT. +] and either couple to o ions or capture electron and become interstitial alkali atom, leaving, further, [ALO IND. 4] POT. 0 hole center. Heating at about 300 GRAUS C electrons from M POT 0 or M POT +O POT recombine with holes in [ALO IND. 4] POT. 0, emitting TL light, besides regrouping Al POT. 3+ and M POT. + to reform [Al POT. 3+/M POT. +] system by coulomb attraction. The electrodiffusion experiment was extended to beryl crystal, because beryl has also structural channels. To explain initial sweeping current behaviour as well as thermoluminescent property a mechanism involving [FE POT. 3+/M POT. +] system is proposed.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16816号 / 工博第3537号 / 新制||工||1535(附属図書館) / 29491 / 京都大学大学院工学研究科社会基盤工学専攻 / (主査)教授 松岡 俊文, 教授 垣内 隆, 准教授 西山 哲 / 学位規則第4条第1項該当

The Areachap Group represents a mid-Proterozoic fossil island arc environment consisting of amphibolite, hornblende gneiss, quartz-feldspathic gneiss, calcsilicates and pelitic schists. Chemical compositions of these highly deformed upper amphibolite/granulite grade metamorphosed rocks indicate protoliths ranging from rhyolite/rhyodacite, calc-alkaline basalt, tholeiite to ultramafic igneous rocks and sediments. The above-mentioned assemblage is typical of an island arc environment. Island arc environments are ideal hosts for volcanic hosted massive sulphide (VHMS) type deposits and may successfully be explored by using the VHMS lithogeochemical alteration model. VHMS deposits not only yield strategic base metals such as zinc (Zn), copper (Cu) and lead (Pb), but significant grades of gold (Au) and silver (Ag) are associated with these deposits. The Areachap Group presents a metallogenic province containing one economic deposit, the Prieska Zn-Cu mine, as well as several sub-economic deposits, including the Areachap mine and other lesser prospects at Boksputs, Kantienpan, Jacomynspan and Rokoptel. The Prieska Zn-Cu mine is the most significant VHMS deposit of the Areachap Group and occurs within the Copperton volcanic centre. This abandoned mine delivered 47 Mt sulphide ore at 1,7 % Cu and 3,8 % Zn with traces of Ag and Au. Four volcanic centres were previously identified in the Areachap Group, namely Upington, Klein Begin, Boksputs and Copperton. Exploration activities were loosely subdivided into the same regions. Regional lithogeochemical sampling campaigns were conducted for the four subproject areas and approximately 5 000 rock samples were analysed for the twelve major oxides and ten trace elements. The region of interest, the Boksputs Subvolcanic area, with a well-established infrastructure, is situated near Groblershoop (50 km east) and Marydale (30 km southeast) in the Northern Cape province and is part of the geological Areachap Group. Several high copper anomalies and the tholeiitic lithological composition of the Boksputs Subproject resulted in this area being selected as the main target region. It was attempted to discriminate between different trace element populations using probability plots, but this was not successful. The complexity of the probability plots was attributed to the large variation in different rock types included in the data set. Corrections were made by determining threshold values for each rock type, but this refinement proved unsuccessful, indicating that the rock classification used was incorrect. Option areas were finally selected, based primarily on absolute Cu values. These areas were mapped in . more detail prior to ground electromagnetic (EM) surveys and drilling. To test the target selection, a proto-lithological map of the area, based on cluster analyses of the lithogeochemical dataset, was drawn. The proto-lithological maps formed the basis of the follow-up work and the application of the VHMS conceptual model. A conductor in the Kantienpan target area was located with a time domain electromagnetic (TDEM) survey and this was drilled. The drilling intersected a massive sulphide body with a tonnage of approximately 5 Mt and an average grade of 4.09 % Zn, 0.49 % Cu and traces of Au and Ag. The orebody was evaluated financially and it was found to be uneconomic as a stand-alone operation. However, if the Kantienpan deposit is considered as an alternative to imported concentrate for the Zincor smelter, this study suggests that the project may be economically feasible. Furthermore, it must be stated that the Areachap Group remains only partly explored and that a world class VHMS deposit may be discovered within the next few years. / Dissertation (MSc)--University of Pretoria, 2008. / Geology / unrestricted

Orientadores: Carlos Kenichi Suzuki, Jacinta Enzweiler / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-24T12:58:32Z (GMT). No. of bitstreams: 1 Santos_MuriloFerreiraMarquesdos_M.pdf: 35876462 bytes, checksum: 9ccb2d6d6d03821c52795bf16da4325e (MD5) Previous issue date: 2014 / Resumo: Este trabalho foi conduzido com base em avaliar o potencial de jazidas de quartzo localizadas no Brasil para a utilização na fabricação de sílica vítrea para as indústrias de alta tecnologia (principalmente focando a manufatura de utensílios para a purificação e processamento de silício e de vidro óptico transparente no UV). As jazidas foram escolhidas conforme sua importância econômica no passado, seus níveis de produção, sua pureza química e a disponibilidade de minério. Elas foram avaliadas quanto à sua geologia, composição química (pela técnica de ICP-MS) e comportamento quando submetidas à fusão em sílica vítrea. Para esta fusão duas técnicas foram utilizadas, a técnica de Verneuil e a fusão em plasma pulsado (Spark Plasma Sintering). Os vidros fundidos com o material de cada jazida foram caracterizados quanto à transmitância óptica no visível e no UV. O trabalho também buscou identificar qual seria a melhor maneira de processar industrialmente o mineral proveniente de cada jazida. Os resultados obtidos mostram que várias jazidas são capazes de produzir vidros de alta qualidade, em especial aqueles provenientes de amostras da formação Serra de Santa Helena, localizada no norte do Estado de Minas Gerais e de Brotas de Macaúbas, no Estado da Bahia. Outras jazidas localizadas no Estado da Bahia também se mostraram alternativas economicamente viáveis / Abstract: This work aimed to evaluate the use of Brazilian quartz in the manufacture of silica glass for high tech industries (specially focused in the production of quartz crucibles for the high purity silicon industry and in the production of optical glass transparent to UV radiation). The mines which were studied here were selected according to its economic importance in the past, its production levels, its chemical purity and the amount of mineral contained in it. All mines were evaluated according to its geology, its chemistry (using the ICP-MS technique), and its behavior during fusion. In order to conduct this fusion, two different fusion techniques were used: Verneuil method, for flame fusion, and Spark Plasma Sintering (SPS) for electrical fusion. After fusion, each glass was evaluated according to its optical transmittance. It was also proposed some ways of industrially processing the minerals in order to obtain a better powder for fusion. Obtained results show that Brazilian mines are highly capable of producing good quality glasses using simple processing methods. The work emphasize the quality of the minerals original from the Santa Helena Formation, in northern Minas Gerais State, and from Brotas de Macaúbas, in the State of Bahia. Other minerals from the state of Bahia might also be a viable alternative / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Orientadores: Eduardo Tavares Costa, André Oliveira Sawakuchi / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-27T00:20:49Z (GMT). No. of bitstreams: 1 Mineli_ThaysDesiree_M.pdf: 1544477 bytes, checksum: 80869854299a120a6e91842425c1e644 (MD5) Previous issue date: 2015 / Resumo: O uso de radiação ionizante é cada vez mais intenso, seja na indústria seja na área médica. Os efeitos nocivos da radiação ionizante exigem medidas de segurança na sua utilização e um dos meios mais comuns para proteção da saúde do operador de equipamentos que usam esta radiação é o controle da dose que este pode receber em determinado período de tempo. Para tal controle, são normalmente utilizados dosímetros pessoais. Estudos sobre datação de sedimentos costeiros e fluviais do Brasil têm encontrado tipos específicos de quartzo com excelentes características dosimétricas. Com o objetivo de analisar as propriedades dosimétricas de amostras de quartzo de elevada sensibilidade de luminescência e avaliar a sua possível utilização na dosimetria pessoal, foram feitos testes comparativos com amostra do principal e mais utilizado dosímetro pessoal do tipo OSL (Optically Stimulated Luminescence), o Al2O3:C. Este trabalho apresenta as características de luminescência de amostras de quartzo. Essas características foram determinadas por testes de recuperação de dose conhecida (dose recovery) por meio de protocolo de alíquota única (Single-Aliquot Regenerative ¿ SAR) em amostras irradiadas por fonte de radiação beta. Foram realizados testes de sensibilidade e de estabilidade do sinal OSL e testes com radiação gama. Os resultados mostraram que as amostras de quartzo estudadas foram capazes de recuperar com exatidão doses de 50 mGy a 50Gy. Estimou-se que as amostras de quartzo saturam em doses (114-175 Gy) superiores à dose de saturação da amostra de Al2O3:C (35 Gy). A dose mínima capaz de ser medida pelas amostras de quartzo variou de 0,2 mGy (para radiação gama) a aproximadamente 20 mGy (para radiação beta). As amostras de quartzo não apresentaram fading do sinal OSL. O sinal OSL ultravioleta da amostra de Al2O3:C cresceu com o tempo. A amostra de Al2O3:C apresentou maior sensibilidade em comparação às amostras de quartzo no teste com radiação beta. A sensibilidade da amostra de quartzo TE65B no teste com radiação gama foi superior à sensibilidade da amostra Al2O3:C. Estes resultados indicam que as amostras de quartzo estudadas têm potencial como material para dosímetros e incentivam estudos mais aprofundados para avaliar o uso destes tipos de quartzo como elementos sensores em dosímetros pessoais / Abstract: The use of ionizing radiation is becoming more intense, whether in industry or in the medical field. The harmful effects of ionizing radiation require safety measures in its use. One of the most common ways to protect the health of the operator of ionizing radiation equipment is the dose control that he/she can receive in a given time period. Personal dosimeters are used for this purpose. Studies on dating of coastal and fluvial sediments in Brazil have found quartz types with very high luminescence signal and excellent dosimetric characteristics. In order to analyze the dosimetric properties of very bright Brazilian quartz samples and evaluate their use in personal dosimetry, comparative tests with the most used personal OSL (Optically Stimulated Luminescence) dosimeter, Al2O3:C, were made. This work presents the luminescence characteristics of quartz samples. These characteristics were determined by dose recovery tests using a Single-Aliquot Regenerative dose protocol (SAR) in samples irradiated by beta radiation. Sensitivity and stability tests and gamma radiation tests were made. The results have shown that the studied quartz samples were able to recover at least a dose range from 50 mGy to 50 Gy. It was estimated that the quartz samples saturate in doses (114-175 Gy) above the saturation dose of Al2O3:C sample (35 Gy). The minimum dose capable of being measured by the quartz samples ranged from 0.2 mGy (for gamma rays) to about 20 mGy (for beta radiation). The quartz samples showed no fading of the OSL signal. The ultraviolet OSL signal of Al2O3:C sample increased with time. The Al2O3:C sample showed higher sensitivity compared to quartz samples in beta radiation test. However, the sensitivity of TE65B quartz sample for the gamma radiation test was higher than the sensitivity of the Al2O3:C sample. These results indicate that the studied quartz samples have potential as dosimeter material and encourage further studies to evaluate the use of this type of quartz as sensor element in personal dosimeters / Mestrado / Engenharia Biomedica / Mestra em Engenharia Elétrica

The Himalayan orogen provides a natural laboratory to test models of orogenic development due to large-scale continental collision. The Greater Himalayan Series (GHS), a lithotectonic unit continuous along the entire length of the belt, comprises the metamorphic core of the Himalayan orogen and underlies the highest topography. GHS rocks are exposed as a moderately north-dipping slab bounded below by the Main Central Thrust (MCT) and above by the South Tibetan Detachment System (STDS) of normal faults. Coeval reverse- and normal-sense motion on the crustal-scale MCT and STDS ductile shear zones allows the GHS to be modeled as an extruded wedge or channel of mid-crustal material. Due to this unique tectonic setting, the deformation path of rocks within the bounding shear zones and throughout the core of the GHS profoundly influences the efficiency of extrusion and exhumation processes. Attempts to quantify GHS deformation and metamorphic evolution have provided significant insight into Himalayan orogenic development, but these structural and petrologic studies are often conducted in isolation. Penetrative deformation fabrics developed under mid-upper amphibolite facies conditions within the GHS argue that deformation and metamorphism were coupled, and this should be considered in studies aimed at quantifying GHS teconometamorphic evolution. This work focuses on two projects related to the coupled deformation, thermal and metamorphic evolution during extrusion and exhumation of the GHS, focused on the lower and upper margins of the slab. A detailed examination of the P--T history of a schist collected from within the MCT zone of the Sutlej River, NW India, provides insight into the path experienced by these rocks as they traveled through the crust in response to the extreme shortening related to India-Asia collision. Combined forward thermodynamic and diffusion modeling indicates compositional zoning preserved in garnet has remained unmodified since growth and can be related directly to the P--T--X evolution of rocks from this zone. Classic porphyroblast--matrix relationships coupled with the above models provide a structural framework within which to interpret the microstructures and provide additional constraints on the relative timing of metamorphic and deformation events. A combined microstructural and quartz petrofabric study of rocks from the highest structural levels of the GHS in the Zanskar region was completed. This work provides the first quantitative estimate of temperatures attending normal-sense shearing along the Zanskar Shear Zone, the westernmost strand of the STDS. Results indicate penetrative top-N (extensional) deformation occurred at elevated temperatures and resulted in the telescoping of isothermal surfaces present during shearing and extrusion of GHS rocks. Simple geometric models invoking heterogeneous simple shear parallel to the overlying detachment require dip-slip displacement magnitudes on the order of 15--40 km, identical to estimates derived from nearby barometric analyses. Finally, focus is given to the rotational behavior of rigid inclusions suspended in a flowing viscous matrix from a theoretical perspective. Predictions of clast rotational behavior have been used to construct several kinematic vorticity estimation techniques that have become widely adopted for quantitative studies of naturally deformed rocks. Despite the popularity of the techniques, however, basic questions regarding clast-based analyses remain open. Therefore a numerical model was constructed and a systematic investigation of 2- and 3D clasts suspended in steady and non-steady plane-strain flows was undertaken to determine likely sources of error and the intrinsic strengths and limitations of the techniques. / Ph. D.

No description available.

The objective of this research work is to investigate the practicality of magnetic workholding of non-magnetic synthetic quartz during high-speed grinding. This research work is sponsored by Quartzdyne and will be used as the starting point to applying single-piece rounding of its quartz. Hypotheses were created that would permit the authors to conclude that magnets are in fact worthwhile workholders for non-magnetic materials. Designs of Experiments were used to reject or fail to reject the null hypotheses. Experiments were carried out using a custom HAAS lathe, modified into a grinding center with an NSK live spindle, and neodymium-iron-boron magnets used to obtain both the holding and shear forces. Lastly, purchased polyolefin foam bumpers were used to increase the shear force, values were obtained with the Starrett force measurement machine. Input variables for the Design of Experiments (DOE) comprised of the holding force, feed-rate, part rotation, and in-feed size of cuts. Sample rotation relative to the magnets was the singular output variable. Experimental results were fitted with the correct distribution and modeled. Once a statistically significant model was attained input settings that minimized quartz sample rotation were determined and used to create an optimized program. Two sets of experiments were needed before the data could be properly fitted with a model. Thirteen out of fifteen samples remained stationary during the optimized program, which was adequate in failing to reject the second null hypothesis; a static sample at 350 RPM will remain static when undergoing high-speed rounding of its outside perimeter. Comparison of cycle times was crucial in reaching this conclusion; in fact, the cycle time of 7 minutes and 58 seconds for the optimized program was substantially less than Quartzdyne's estimated batch flow per piece cycle time of around 15 minutes. Obtaining a model was not possible or needed for the first hypothesis due to all experiments having zero rotation, therefore the authors also failed to reject the first null hypothesis; a static sample sandwiched between two permanent magnets with adequate holding force will remain stationary during rotation (min 250 RPM) Larger in-feed size cuts are possible when the quartz is square in shape –interrupted cuts. As it becomes cylindrical, cuts were reduced to experimental levels. Also, due to the amount of material being removed, the resin bonded wheel required dressing, without it rotation is expected. Variation was noticed while quantifying the shear force; it is attributed to the polyolefin foam bumper with its inconsistent coefficient of friction. A more uniform material, which can provide repeatable shear force values, would lessen the variation. All optimized program samples turned out perfectly round- even the two that had slight rotation.