Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-23T11:02:37Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-23T11:02:37Z (GMT). No. of bitstreams: 0 / O sistema Cananéia-Iguape é um grande complexo de canais lagunares e estuarinos, localizado no sul do estado de São Paulo. Este sistema passou a receber as águas do rio Ribeira de Iguape após a abertura do canal do Valo Grande, finalizado no ano de 1852. Este canal tornou-se a principal rota de transporte das produções da região do Vale do Ribeira, e nas décadas de 1940 a 1990 as atividades de mineração da região contaminaram o rio Riberia de Iguape, causando alterações nas características originais do sistema Cananéia-Iguape. Este estudo avaliou os níveis de urânio e tório nas amostras de sedimentos superficiais deste sistema. Esta avaliação foi feita através de um método espectrofotométrico utilizando Arsenazo III. As amostras foram digeridas em um forno micro-ondas com aplicação de HNO3, HF e H2O2. As concentrações de urânio variam de 1,3 mg·kg-1 a 5,8 mg·kg-1 e as de tório de 0,82 mg·kg-1 a 12,1 mg·kg-1. Estes resultados foram comparados com os dados da região, e observou-se que as concentrações determinadas são similares. O índice de geoacumulação foi calculado, classificando a região como \"Não contaminada a moderadamente contaminada\" para urânio e \"Não contaminada\" para tório, indicando que não há contaminação por estes metais. Estes resultados podem ser considerados como a concentração basal da região. As avaliações estatísticas identificaram uma maior afinidade do urânio e do tório com a fração de argila e silte. As concentrações de U e Th não apresentaram um comportamento homogêneo ao longo do sistema estudado. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Submitted by Rosangela Silva (rosangela.silva3@unioeste.br) on 2018-05-15T19:35:27Z No. of bitstreams: 2 Saulo Vinicius da Rosa.pdf: 2244692 bytes, checksum: e13fed6b2f75e2fa2861bf064a121ca7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-05-15T19:35:27Z (GMT). No. of bitstreams: 2 Saulo Vinicius da Rosa.pdf: 2244692 bytes, checksum: e13fed6b2f75e2fa2861bf064a121ca7 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-03-03 / Bulk fill resins can be used as dentin replacements, requiring coating by another composite resin, such as a nano-hybrid resin, or they can be used without the need for a new composite resin for their protection. The objective of this work was to evaluate the bond strength of repairs made between different composite resins, after aging in different solutions. Five composite resins were used, one conventional and four bulk fill composites. 2x2x5 mm CP were made in silicone mold and aged for 30 days, after which the resins were given the surface treatment and soon after the repair, becoming a CP with 2x2x10mm. All the resins were combined. The mean values obtained for each test specimen were submitted to the Shapiro Kruskall Wallis test, followed by the Dunn test, p <0.05. The results showed that, after aging in distilled water, Aura bulk fill as base showed statistical differences when compared to the composite resins Z350 (1.27 + 0.95) and Tetric Ceram bulk fill (3.72 + 1.74), the composite resin Tetric Ceram bulk fill used as a base showed that there was statistical difference when Filtek bulk fill composite resin 4,81 (+1,20) was used and when Z350 resin (2.22 + 0.63) and Tetric Ceram bulk fill (2.54 + 0.52). After aging in water / ethanol solution, no statistically significant differences were found between all possible combinations. After aging in nitric acid solution, when Aura bulk fill was used as base there were statistical differences between the repair with Tetric Ceram bulk fill (4.02 + 0.82) and Z350 (1.71 + 1.09 ), when Filtek bulk fill used as base there were statistical differences between Z350 (2.30 + 0.62) and Filtek bulk fill 4.02 (+1.85) used for the repair, with Tetric ceram bulk fill as base there were statistical differences when compared to the composite resin Filtek bulk fill 4,04 (+1,07) and Z350 (1,99 + 0,76). According to the results obtained it was possible to verify that, in the majority of the comparisons made among the composite resins evaluated in this study, the composite resins bulk fill obtained better values of bond strength when the composite resins themselves were united bulk fill and the worst values when they received the repair with the composite resin when immersed in acidic solutions and distilled water, it was not possible to observe statistically significant differences when immersing in water / ethane. / As resinas “bulk fill” podem ser utilizadas como substitutas da dentina, necessitando de recobrimento por outra resina composta, como uma resina nano- híbrida, ou ainda podem ser utilizadas sem a necessidade de uma nova resina composta para sua proteção. O objetivo desse trabalho foi avaliar a resistência de união de reparos confeccionados entre diferentes resinas compostas, após envelhecimento em diferentes soluções. Foram utilizadas cinco resinas compostas, sendo uma convencional e quatro resinas compostas “bulk fill”. Foram confeccionados CP de 2x2x5 mm em molde de silicone e envelhecidas por 30 dias, após esse período as resinas receberam o tratamento de superfície e logo após o reparo, tornando-se um CP com 2x2x10mm. Todas as resinas foram combinadas entre si. Os valores médios obtidos para cada corpo de prova foram submetidos ao teste de Shapiro Kruskall Wallis, seguido do pós teste de Dunn, p < 0,05. Os resultados mostraram que após o envelhecimento em água destilada, a Aura bulk fill como base mostrou diferenças estatísticas quando comparadas as resinas compostas Z350 (1,27+0,95) e Tetric Ceram bulk fill (3,72+1,74), a resina composta Tetric Ceram bulk fill utilizada como base mostrou que houve diferença estatística quando utilizada a resina composta Filtek bulk fill 4,81(+1,20) e quando utilizada a resina Z350 (2,22+0,63) e Tetric Ceram bulk fill (2,54+0,52). Após o envelhecimento em solução água/etanol não foram encontradas diferenças estatisticamente significantes entre todas as combinações possíveis. Após o envelhecimento em solução de ácido nítrico, quando a Aura bulk fill foi utilizada como base houve diferenças estatísticas entre o reparo com a Tetric Ceram bulk fill (4,02+0,82) e a Z350 (1,71+1,09), já quando Filtek bulk fill utilizada como base houve diferenças estatísticas entre a Z350 (2,30+0,62) que e a Filtek bulk fill 4,02(+1,85) usadas para o reparo, com a Tetric ceram bulk fill como base houve diferenças estatísticas quando comparadas a resina composta Filtek bulk fill 4,04(+1,07) e a Z350 (1,99+0,76). De acordo com os resultados obtidos foi possível verificar que, na maioria das comparações realizadas entre as resinas compostas avaliadas nesse estudo, as resinas compostas bulk fill obtiveram melhores valores de resistência a união quando unidas as próprias resinas compostas bulk fill e os piores valores quando receberam o reparo com a resina composta quando imersas em soluções ácidas e na água destilada, já na imersão em água/etano não foi possível observar diferenças estatisticamente significantes.

A chemical ionisation mass spectrometer (CIMS) was developed and utilised for measurements onboard the Facility for Atmospheric Airborne Measurements (FAAM) BAe-146 aircraft. The I- ionisation scheme was implemented to detect nitric acid (HNO3), formic acid (HC(O)OH), hydrogen cyanide (HCN) and dinitrogen pentoxide (N2O5) simultaneously at a sampling frequency of 1 Hz. Sensitivities ranged from 35±6 ion counts pptv-1 s-1 for HC(O)OH to 4±0.9 ion counts pptv-1 s-1 for HCN and limits of detection from 37 ppt for HNO3 and 5 ppt for HCN. Trace gas concentrations of species such as HC(O)OH are currently under predicted in global models. In order to understand their role in controlling air quality, it is crucial that their production pathways and abundance are accurately measured and constrained. To date, airborne measurements of these trace gases have been difficult as a result of instrumental limitations on an aircraft such as limit of detection and sampling frequency. The first UK airborne measurements of HC(O)OH and HNO3 confirmed that HC(O)OH is under predicted by up to a factor of 2 in a trajectory model that implements the full Master Chemical Mechanism (MCM) and Common Representative Intermediate Scheme (CRI). The inclusion of a primary vehicle source enabled the model to reproduce the concentrations observed; verifying that direct sources are under represented. Secondary formation of HC(O)OH was observed through its correlation with HNO3 and ozone (O3), indicating a strong photochemical production source. Hydroxyl (OH) concentrations were estimated for the first time in a flight around the UK using the HC(O)OH and HNO3 measurements. A biomass burning (BB) plume identification technique is applied to data obtained from Canadian biomass fires using HCN as a marker. A 6 sigma above background approach to defining a plume resulted in a higher R2 correlating value for the normalised excess mixing ratio (NEMR) to carbon monoxide (CO) when compared to current methods in the literature. The NEMR obtained from this work; 3.76±0.02 pptv ppbv-1, lies within the range found in the literature. This NEMR is then used to calculate a global emission total for HCN of 0.92 Tg (N) yr-1 when incorporated into the global tropospheric model STOCHEM CRI. The first direct N2O5 airborne measurements on an aircraft at night are compared to indirect measurements taken by a broadband cavity enhancement absorption spectrometer. An average R2 correlation coefficient of 0.87 observed over 8 flights for 1 Hz measurements indicates the selectiveness of the I- ionisation scheme to detect N2O5 directly, without nitrate (NO3) interference.

This work examines an electrochemical determination of mixed nitric and sulphuric acid solution that is formed during calorimetric determination of gross calorific value of coal carried out under the ISO 1928:1995 standard. Knowing the amount of these acids is necessary for calculating net calorific value. The named standard only allows use of volumetric methods which are time-consuming. Conductivity and ion-selective measurements were used here which significantly shortened analysis time. Overall conductivity measurement was taken with a 4-electrode meter while nitric acid was measured with a nitrate ISE by known addition method. Sulphuric acid was then calculated according to actual temperature. This research has defined the calibration relations and temperature effect. Several simulated and real-world samples were analysed and the method was evaluated for a possible use in a future automated analyser.

There are two parts in this study. The first part is to test the validity of the assumption of thermodynamic equilibrium between fine particulate (PM2.5) nitrate and ammonium and gas-phase nitric acid (HNO3(g)) and ammonia (NH3(g)). A rough estimation of the characteristic time to achieve thermodynamic equilibrium is first carried out, which suggests that PM2.5 and gas-phase species are in thermodynamic equilibrium. Then equilibrium is tested by calculating the equilibrium concentrations of HNO3(g) and NH3(g) implied by the PM2.5 inorganic composition, temperature and relative humidity observed at the Atlanta Supersite 1999 using ISORROPIA model. The second part of this study is to analyze the ground-level ozone pollution precursor relationships in Hong Kong area. Characteristics of O3 precursors are explored. Trace gases NO and CO, VOCs, absorption coefficient, temperature and solar radiation are associated with the O3 formation. Specific VOC and VOC-sources that contribute most to the formation of photochemical smog are identified. The accuracy of pollutant emission inventories for Hong Kong and PRD region is also assessed. Combined with back trajectory information, dCO/dNOy is used to define whether O3 is locally or regionally occurred. An OBM is used to investigate the relative benefits of various emission-control strategies. Generally the formation of O3 throughout much of Hong Kong area is limited by VOC, in which reactive aromatics are dominant.

Die vorliegende Arbeit befasst sich mit der grundlegenden Untersuchung von Reaktionsmustern kristalliner Si-Oberflächen in HF-basierten Lösungen. Ausgehend von den industriell genutzten HF-HNO3-H2O-Gemischen wurden wisher wenig untersuchte HF/HNO3-Konzentrationsverhältnisse, die durch gelöste Stickoxide bedingten Folgereaktionen sowie der PH-Wert als Steuerparameter zur Aufarbeitung feinkörniger Si-Rohstoffe (Korngröße ≤ 0,5 mm) identifiziert. Die in diesem Kontext zentrale Rolle der NO+-Ionen wurde durch Untersuchung der spezifischen Reaktionsmuster an kristallinen as-cut und hydrophobierten Si-Oberflächen sowie bei Umsetzungen mit Oligosilanen als Modellverbindungen bestätigt. Die aus den umfassenden analytischen Daten (FT-IR-, Raman-, NMR-Spektroskopie, IC, REM-EDX, AFM) gewonnenen Erkenntnisse liefern einen wichtigen Beitrag zum Verständnis nasschemischer Halbleiterätzprozesse und erschließen neue Anwendungsfelder.

Opération de tête des procédés hydrométallurgiques de recyclage des combustibles nucléaires usés, la dissolution est une étape importante : la mise en solution des éléments chimiques est indispensable avant la réalisation des étapes d’extraction liquide-liquide permettant de faire le tri entre matière valorisable et déchets ultimes. Cette étude a pour objectif de mieux appréhender les phénomènes chimiques, physico-chimiques et hydrodynamiques de la réaction de dissolution du dioxyde d’uranium en milieu nitrique. Elle s’inscrit dans une démarche de modélisation du procédé par l’expression des vitesses intrinsèques de réaction et la description des phénomènes physico-chimiques aux interfaces. Une approche par microscopie optique a permis de confirmer le caractère fortement autocatalytique de la réaction et de mesurer, pour la première fois, les vitesses « vraies » de la réaction chimique. L’attaque des massifs, obtenus par frittage, se fait par des sites préférentiels d’attaque et entraîne le développement de failles dans les massifs qui peuvent aller jusqu’à déliter le massif. Cette attaque non uniforme est rendue possible par l’établissement d’un bullage dans ces failles qui permet un renouvellement périodiquement des réactifs et entretient la réaction en leur sein. Ce point constitue un élément clef du mécanisme : un lien fort entre développement des failles, bullage dans les failles, et vitesses de dissolution globales est mis en évidence dans ce travail. Enfin, un modèle intégrant les bilans couplés de matière liés à l’évolution structurelle du solide et des compositions en phase liquide, et tenant compte du transport aux interfaces, est proposé. Les simulations fondées sur ce modèle sont proches des observations expérimentales, et permettent de reproduire pour la première fois l’effet de différents paramètres réactionnels, comme celui de la diminution des cinétiques lors d’une augmentation de la turbulence / Dissolution is a milestone of the head-end of hydrometallurgical processes used for recycling spent nuclear fuel. The solubilization of the chemical elements is essential before performing the liquid-liquid extraction steps to separate reusable material and final waste. This study aims at better understanding the chemical, physico-chemical and hydrodynamic phenomena of uranium dioxide dissolution reactions in nitric medium. This study is also part of a modeling approach aiming at expressing the intrinsic reaction rates and describing of the physico-chemical phenomena at interfaces. Optical microscopy confirmed the highly autocatalytic nature of the reaction and led to measurements, for the very first time, of "true" chemical kinetics of the reaction. The acid attack of sintering-manufactured solids occurs through preferential attack sites. It develops cracks in the solids that can lead to the cleavage of the solid. This inhomogeneous attack is made possible by the establishment of bubbling in the cracks which allows periodic renewal of the reagents and thus maintains the reaction within the cracks. This point is a key component of the mechanism: a strong link between the development of cracks, bubbling through the cracks, and overall dissolution kinetics is demonstrated in this work. Finally, a model coupling material balance to the structural evolution of the solid and liquid phase compositions, and taking into account the interfacial transport is proposed. The simulations based on this model are close to the experimental observations, and allow to reproduce for the very the first time the effect of various reaction parameters, such as the reduction of overall kinetics when turbulence increases

Die vorliegende Arbeit befasst sich mit der grundlegenden Untersuchung von Reaktionsmustern kristalliner Si-Oberflächen in HF-basierten Lösungen. Ausgehend von den industriell genutzten HF-HNO3-H2O-Gemischen wurden wisher wenig untersuchte HF/HNO3-Konzentrationsverhältnisse, die durch gelöste Stickoxide bedingten Folgereaktionen sowie der PH-Wert als Steuerparameter zur Aufarbeitung feinkörniger Si-Rohstoffe (Korngröße ≤ 0,5 mm) identifiziert. Die in diesem Kontext zentrale Rolle der NO+-Ionen wurde durch Untersuchung der spezifischen Reaktionsmuster an kristallinen as-cut und hydrophobierten Si-Oberflächen sowie bei Umsetzungen mit Oligosilanen als Modellverbindungen bestätigt. Die aus den umfassenden analytischen Daten (FT-IR-, Raman-, NMR-Spektroskopie, IC, REM-EDX, AFM) gewonnenen Erkenntnisse liefern einen wichtigen Beitrag zum Verständnis nasschemischer Halbleiterätzprozesse und erschließen neue Anwendungsfelder.

В представленной работе на тему «Исследование комбинированной технологии переработки медно-цинковых промпродуктов» произведены теоретические и лабораторные исследования по определению оптимальной технологии переработки медно-цинковых сульфидных промпродуктов гидрометаллургическим способом. Рассмотрены две эффективные технологии, проведено сравнение по объективным показателям, сделаны экологоэкономический и экономический расчеты. / In this study, entitled "Study of the combined technologies of processing of copper-zinc middlings" produced theoretical and laboratory studies to determine the best technology processing of copper-zinc sulphide middlings hydro- metallurgical method. Two efficient technologies are considered, compared to objective indicators, are made of ecological, and economic calculations.

The deteriorating air quality in Cape Town (CT) is a threat to the social and economic development of the city. Although previous studies have shown that most of the pollutants are emitted in the city, it is not clear how the transport of pollutants from neighbouring cities may contribute to the pollution. This thesis studies the transport of atmospheric nitrogen oxides (NOx) and nitric acid (HNO3) pollutants over South Africa and examines the role of pollutant transport from the Mpumalanga Highveld on pollution in CT. The study analysed observation data (2001 - 2008) from the CT air quality network and from regional climate model simulation (2001 - 2004) over South Africa. The model simulations account for the influences of complex topography, atmospheric conditions, and atmospheric chemistry on transport of the pollutants over South Africa. Flux budget analysis was used to examine whether the city is a net source or sink for NOx and HNO3. The results show that north-easterly flow transports pollutants (NOx and HNO3) at low level (i.e., surface to 850 hPa) from the Mpumalanga Highveld towards CT. In April, a tongue of high concentration of HNO3 extends from the Mpumalanga Highveld to CT, along the southern coast. The flux budget analysis shows that CT can be a net sink for NOx and HNO3 during extreme pollution events. The study infers that, apart from the local emission of the pollutants in CT, the accumulation of pollutants transported from other areas may contribute to pollution in the city. / Environmental Sciences / M. Sc. (Environmental Science)