名古屋大学年代測定総合研究センターシンポジウム報告

L’objet de la présente étude est le développement, l’application et la diffusion de la technologie associée à divers types d’alliages de cuivre, en particulier l’alliage du plomb-bronze, en Grèce ancienne, dans ses colonies, ainsi qu’en Étrurie. Le plomb-bronze est un mélange de diverses proportions d’étain, de cuivre et de plomb. Le consensus général chez les archéométallurgistes est que le plomb-bronze n’était pas communément utilisé en Grèce avant la période hellénistique; par conséquent, cet alliage a reçu très peu d’attention dans les documents d’archéologie. Cependant, les analyses métallographiques ont prouvé que les objets composés de plomb ajouté au bronze ont connu une distribution étendue. Ces analyses ont aussi permis de différencier la composition des alliages utilisés dans la fabrication de divers types de bronzes, une preuve tangible que les métallurgistes faisaient la distinction entre les propriétés du bronze d’étain et celles du plomb-bronze. La connaissance de leurs différentes caractéristiques de travail permettait aux travailleurs du bronze de choisir, dans bien des cas, l’alliage approprié pour une utilisation particulière. L’influence des pratiques métallurgiques du Proche-Orient a produit des variations tant dans les formes artistiques que dans les compositions des alliages de bronze grecs durant les périodes géométrique tardive et orientalisante. L’utilisation du plomb-bronze dans des types particuliers d’objets coulés montre une tendance à la hausse à partir de la période orientalisante, culminant dans la période hellénistique tardive, lorsque le bronze à teneur élevée en plomb est devenu un alliage commun. La présente étude analyse les données métallographiques de la catégorie des objets coulés en bronze et en plomb-bronze. Elle démontre que, bien que l’utilisation du plomb-bronze n’était pas aussi commune que celle du bronze d’étain, il s’agissait néanmoins d’un mélange important d’anciennes pratiques métallurgiques. Les ères couvertes sont comprises entre les périodes géométrique et hellénistique. / The subject of this study is the development, application and diffusion of the technology of various types of copper alloys, particularly that of leaded bronze, in ancient Greece, its colonies, and in Etruria. Leaded bronze is a mixture of tin, copper and lead in various proportions. The general consensus among archaeometallurgists is that leaded bronze was not commonly used in Greece until the Hellenistic period, and thus this alloy has not received very much attention in archaeological literature. However, metallographic analyses demonstrate that objects composed of leaded bronze had a wide distribution. The analyses also show differentiation in the composition of alloys that were used in the manufacture of various types of bronzes, a tangible indication that metalworkers distinguished between the properties of both tin bronze and leaded bronze. The knowledge of their different working characteristics is what enabled a bronzeworker to choose, in many cases, the appropriate alloy for a specific application. The influence of Near Eastern metallurgical practices produced variations in both the artistic forms as well as alloy compositions of Greek bronzes during the Late Geometric and Orientalizing periods. The use of leaded bronze for particular types of cast objects shows an increasing tendency from the Orientalizing period onwards, culminating in the late Hellenistic period when high-lead bronze became a common alloy. This study analyzes the metallographic data of specific categories of bronze and leaded bronze cast objects, and it will demonstrate that although the use of leaded bronze was not as prevalent as that of tin bronze, it was nevertheless a significant adjunct of ancient metallurgical practices. The periods surveyed range from the Geometric to the Hellenistic periods.

Um estudo sistemático a respeito da utilização de padrão interno em determinações multielementares por espectrometria de absorção atômica (ETAAS) foi desenvolvido. O objetivo principal do presente trabalho foi verificar a possibilidade de melhorar a precisão e a exatidão dos resultados analíticos, que são obtidos na análise de fluidos biológicos. O pré-tratamento dessas amostras foi simplificado e reduzido a uma única etapa de diluição com surfactante (Triton X-100) e ácido (HNO3). Conseqüentemente, a complexidade da solução diluída de amostra, a ser introduzida no tubo de grafite, apresenta uma elevada quantidade de concomitantes que podem provocar interferências químicas. A seleção preliminar dos elementos a serem testados como padrão interno considerou a semelhança de parâmetros físico-químicos relacionados com o processo de atomização. Desta forma, Ag, Bi, In e Tl foram testados como padrão interno para a determinação simultânea de Cd/Pb em sangue e urina, enquanto Bi, Ge, In, Sb, Sn e Te foram os elementos selecionados para a determinação de Mn/Ni/Se em soro sangüíneo. A melhoria da qualidade dos resultados analíticos obtidos na determinação simultânea de Cd e Pb em sangue foi observada quando Ag foi utilizada como padrão interno, na presença de NH4H2PO4 como modificador químico. Verificou-se uma melhoria na exatidão dos resultados obtidos para Cd e Pb, após a correção com padrão interno. Por outro lado, os resultados obtidos na análise de urina não foram corrigidos por nenhum dos elementos testados. Os melhores resultados para a determinação simultânea de Mn, Ni e Se foram obtidos com a utilização de Bi, Sn e Te como padrão interno. Entretanto, verificou-se que a correção de todos os resultados não seria viável com o uso de um único padrão interno. O melhor desempenho nos testes realizados na presença de soro sangüíneo foi obtido com Bi, que melhorou discretamente a precisão dos resultados obtidos para Se. Desta forma, a padronização interna visando a determinação simultânea de Mn, Ni e Se não foi eficiente. A padronização interna em ETAAS, com a finalidade de melhorar a precisão e a exatidão dos resultados analíticos, é uma estratégia tão complexa, quanto os efeitos interferentes que se pretende corrigir: são necessários mais estudos para compreender melhor como a utilização de uma condição de compromisso afeta os processos de atomização, bem como mais informações a respeito das interferências físicas e químicas causadas por amostras complexas, analisadas por ETAAS após uma simples etapa de diluição. Deve-se considerar com especial atenção o modificador químico e as temperaturas das etapas de pirólise e de atomização empregadas, que são parâmetros críticos para o desempenho de um elemento como padrão interno. / A systematic study involving the use of internal standard for multielement determinations by electrothermal atomic absorption spectrometry was developed. The main objective of this work was evaluate the possibility of improving precision and accuracy of the analytical results for biological fluids. The sample pre-treatment was reduced to a single dilution step with surfactant (Triton X-100) and acid (HNO3), increasing the amount of concomitant introduced into the atomizer. The preliminary selection of the elements to be tested as internal standard considered the resemblance of physico-chemical parameters related with the atomization process. Thus, Ag, Bi, In and Tl were tested as internal standard for the simultaneous determination of Cd/Pb in blood and urine, and Bi, Ge, In, Sb, Sn and Te were the selected elements for the determination of Mn/Ni/Se in blood serum. The correction of the results obtained for the simultaneous determination of Cd and Pb in blood was achieved when Ag was used as internal standard, in presence of NH4H2PO4 as chemical modifier. An improvement for the accuracy of the results was observed for both analytes after their correction with the internal standard. On the other hand, the results obtained for the urine analysis were not corrected by using the tested elements. The best results for the simultaneous determination of Mn, Ni and Se were observed when Bi, Sn and Te were used as internal standard. However, the correction for the results for all analytes was not possible by using only one internal standard. The best performance in presence of the serum was obtained for Bi, which improves slightly the precision for the Se results. Thus, the internal standardization for the simultaneous determination of Mn, Ni and Se was not efficient. The internal standardization in ETAAS, aiming the improvement of precision and accuracy of the analytical results, is a strategy as complex as the interference effects to be corrected: more studies are required in order to better understand how the adoption of a compromised condition disturbs the atomization processes, as well as to get more information about the physical and chemical interference caused by complex samples, analyzed by ETAAS after a single dilution step. The chemical modifier and the selected temperatures for the pyrolysis and atomization steps are critical parameters for the performace of an internal standard and they should be carefully considered.

En Europe, suite à la fermeture de nombreux sites sidérurgiques, une utilisation croissante de laitiers de haut-fourneau d’origine et d’âge variés voit le jour depuis plusieurs années. Cette évolution conduit à une diversification de la composition chimique et minéralogique des laitiers. Connaître l’influence de ces caractéristiques sur la réactivité des laitiers utilisés en substitution du clinker dans les ciments de haut-fourneau (CEM III) devient, dès lors, primordial pour assurer les performances de tels ciments. Dans ce contexte, le présent travail a pour but d’investiguer l’influence de la composition chimique et de l’âge des laitiers sur leur réactivité tant par des essais physico-mécaniques que par une caractérisation physico-chimique et minéralogique de CEM III/B à différentes échéances d’hydratation. L’effet néfaste du vieillissement des laitiers est clairement mis en exergue et son impact diffère selon la composition chimique de départ du laitier. Les ions aluminium engendrent une accélération de l’hydratation et une amélioration des résistances physico-mécaniques à jeune âge mais, à long terme, ils conduisent à une perte de ces dernières. Concernant l’influence des ions titane dans les laitiers, la tendance générale observée est une diminution des performances physico-mécaniques. Sur base de ces résultats, une évaluation de la représentativité de moyens accélérés d’estimation de la réactivité des laitiers est effectuée. Il est mis en évidence que seules les mesures de résistances physico-mécaniques classiques permettent d’évaluer correctement la réactivité des différents laitiers. Une évaluation de la détermination de la teneur en constituants de CEM III/B par la méthode Rietveld est menée par comparaison avec la méthode de dissolution sélective de la norme EN 196-4 et le dosage des constituants par pesée. Moyennant une utilisation adaptée de cette méthode, les résultats obtenus à l’aide de celle-ci sont très encourageants. In Europe, following the closure of many steel plants, an increased use of blast furnace slag (BFS) of various age and origin was born for several years. This evolution leads to a diversification of the chemical and mineralogical composition of the BFS. Knowing the influence of these characteristics on the reactivity of slag used in substitution of clinker in blast-furnace cement (CEM III) becomes, therefore, crucial to ensure the performance of such cements. In this context, this work aims to investigate the influence of chemical composition and age of BFS on their reactivity by both physico-mechanical and physico-chemical and mineralogical characterization of CEM III/B at different times of hydration. The adverse effect of ageing of BFS is clearly highlighted and its impact varies depending on the chemical composition of the BFS. Aluminum ions generate an acceleration of the hydration and improve mechanical strength at early age, but at long term, they lead to a loss of the strength. Regarding the influence of titanium ions in the BFS, the general trend is a decrease of the physical and mechanical performance. Based on these results, an assessment of the representativeness of accelerated means of estimating, the BFS reactivity is done. It is emphasized that only measures of physical and conventional mechanical strength can accurately assess the reactivity of different BFS. An evaluation of the determination of the amount of CEM III/B components by the Rietveld method is based upon comparison with the selective dissolution method from the EN 196-4 norm and components determination by weight. Through appropriate use of this method, the results obtained are very encouraging.

The use of renewable wood-based fuel has been increasing in the last few decades because it is said to be carbon neutral. However, wood-based fuel, and especially used wood (also known as recycled wood or waste wood), is more corrosive than virgin wood (forest fuel), because of higher amounts of chlorine and heavy metals. These elements increase the corrosion problems at the furnace walls where the oxygen level is low. Corrosion mechanisms are usually investigated at the superheaters where the temperature of the material and the oxygen level is higher than at the furnace walls.  Much less work has been performed on furnace wall corrosion in wood or used wood fired boilers, which is the reason for this project.    Tests are also mostly performed under simplified conditions in laboratories, making the results easier to interpret.  In power plants the interpretation is more complicated. Difficulties in the study of corrosion processes are caused by several factors such as deposit composition, flue gas composition, boiler design, and combustion characteristics and so on. Therefore, the laboratory tests should be a complement to the field test ones. This doctoral project involved in-situ testing at the furnace wall of power boilers and may thus contribute to fill the gap. The base material for furnace walls is a low alloy steel, usually 16Mo3, and the tubes may be coated or uncoated. Therefore tests were performed both on 16Mo3 and more highly alloyed materials suitable for protective coatings. Different types of samples exposed in used-wood fired boilers were analysed by different techniques such as LOM (light optical microscopy), XRD (X-ray diffraction), SEM (scanning electron microscopy), EDS (energy dispersive spectroscopy), WDS (wavelength dispersive spectroscopy), FIB (focused ion beam) and GD-OES (glow discharge optical emission spectroscopy). The corrosion rate was measured. The environment was also thermodynamically modelled by TC (Thermo-Calc ®). The results showed that 16Mo3 in the furnace wall region is attacked by HCl, leading to the formation of iron chloride and a simultaneous oxidation of the iron chloride. The iron chloride layer appeared to reach a steady state thickness.   Long term exposures showed that A 625 (nickel chromium alloy) and Kanthal APMT (iron-chromium-aluminium alloy) had the lowest corrosion rate (about 25-30% of the rate for 16Mo3), closely followed by 310S (stainless steel), making these alloys suitable for coating materials. It was found that the different alloys were attacked by different species, although they were exposed in the boiler at the same time in the same place. The dominant corrosion process in the A 625 samples seemed to be by a potassium-lead combination, while lead did not attack the APMT samples. Potassium attacked the alumina layer in the APMT samples, leading to the formation of a low-protective aluminate and chlorine was found to attack the base material.  The results showed that stainless steels are attacked by both mechanisms (Cl- induced attack and K-Pb combination). Decreasing the temperature of the furnace walls of a waste wood fired boiler could decrease the corrosion rate of 16Mo3. However, this low corrosion rate corresponds to a low final steam pressure of the power plant, which in not beneficial for the electrical efficiency. The short term testing results showed that co-firing of sewage sludge with used wood can lead to a reduction in the deposition of K and Cl on the furnace wall during short term testing. This led to corrosion reduction of furnace wall materials and coatings. The alkali chlorides could react with the aluminosilicates in the sludge and be converted to alkali silicates. The chromia layer in A 625 and alumina in APMT were maintained with the addition of sludge. / Förnybara träbaserade bränslen har ökat i användning under de senaste decennierna, eftersom det är koldioxidneutrala. Emellertid är träbaserade bränslen, och i synnerhet använt trä (även känt som återvunnet trä, returträ eller träavfall), mer korrosivt än skogsbränsle, på grund av högre halter klor och tungmetaller. Dessa ökar korrosionsproblemen på eldstadsväggarna, särskilt på platser där syrehalten är låg. Korrosionsmekanismer undersöks vanligtvis på överhettare dvs. på områden där materialets temperatur och syrenivån är högre än vid eldstadsväggarna. Färre arbeten har utförts på eldstadskorrosion i returträ pannor, vilket är motiveringen till detta projekt. Normalt sätt så görs endast i laboratorietester där resultaten är lättare att tolka. I kraftverk är tolkningen mer komplicerad. Undersökningar av korrosionsprocesser försvåras av flera faktorer såsom panndesign, förbränningsegenskaper, rökgassammansättning, beläggningskemi och så vidare. Därför bör laboratorietester kompletteras med fältförsök. Detta doktorandprojekt kan således bidra till att fylla denna brist. Eldstadsväggarna är uppbyggda av flera rör som svetsas samman och de består vanligtvis av 16Mo3 stål. Rören kan vara belagda eller obelagda. Tester har därför genomförts på 16Mo3 samt på höglegerade material vilka är lämpliga som skyddande beläggningar. Olika typer av prov som exponerats i förbränningspannor av returträ analyserades med olika tekniker såsom SEM (svepelektronmikroskopi), EDS (energidispersiv spektroskopi), WDS (våglängd dispersiv spektroskopi), FIB (fokuserad jonstråle) LOM (ljusoptisk mikroskopi), XRD (röntgendiffraktion), och GD-OES (glimurladdning med optisk emissionsspektroskopi). Miljön samt korrosionsprocesser har modellerats termodynamiskt med mjukvaran TC (Termo-Calc®). Resultaten visade att 16Mo3 i eldstadsväggen angrips av väteklorid, vilket leder till bildning av järnklorid och en samtidig oxidation av järnkloriden. Järnkloridskiktet verkade nå ett stationärt tillstånd vad avser tjocklek. Sex veckors prov visade att A 625 (nickelkromlegering) och Kanthal APMT (järnkromaluminiumlegering) hade den lägsta korrosionshastigheten (ca 25-30% av korrosionshastigheten för 16Mo3), följt av 310S (rostfritt stål). Vi har funnit att de olika legeringarna angrips genom olika mekanismer, även om de var exponerade i pannan samtidigt på samma plats. Den dominerande korrosionsmekanismen för legeringen A 625 verkar i huvudsak bero på kalium och bly, medan bly inte attackerar Kanthal APMT. Kalium angriper aluminiumoxidskiktet på Kanthal APMT, vilket leder till bildning av icke-skyddande aluminat medan klor i sin tur attackerar basmaterialet. Resultaten visar att rostfritt stål attackeras genom klor-inducerad korrosion samt kalium och bly i kombination. Reducering av temperaturen kan minska korrosionshastigheten hos 16Mo3. Men denna lägre korrosionshastighet motsvarar ett lågt slutligt ångtryck hos kraftverket, vilket inte är fördelaktigt för elverkningsgraden. De kortare exponeringarna visade att samtidig förbränning av avloppsslam med returträ kan leda till minskad avsättning av kalium och klor i form av alkaliklorider på eldstadsväggarna. Detta ledde till korrosionsminskning av alla studerade material. Dessa alkaliklorider skulle kunna reagera med aluminiumsilikaterna från slammet och omvandlas till alkalisilikater. Detta verkar minska den alkali-inducerade korrosionen på A 625, APMT och 310S. Den aluminiumoxid som bildades på APMT och det kromoxidskikt som bildades på A 625 upprätthölls med tillsats av slam. / <p>QC 20151015</p>

A novel technique for measuring gas temperature and spectral particle emissivity in high-temperature gas-particle streams is presented. The main application of this optical sensor is to improve the process control of batch unit operations, such as steelmaking furnaces. The spectral emission profile of CO and CO2 and the continuous particle emission in the 3.5 to 5 μm wavelength region was recorded and analyzed in real time with a low-resolution passive sensor. The sensor consisted of light collecting optics, a dispersion element (grating spectrometer) and a 64-pixel pyroelectric array. Wavelength and radiance calibrations were performed. The temperature of the gas-particle medium (Tg+p) followed from the least-squares minimization of the difference between the measured radiance in the 4.56-4.7 μm region –which saturates due to the large CO2 concentrations and path lengths in industrial furnaces– and the corresponding blackbody radiance. Particle emissivity (εp) was calculated at 3.95 μm from an asymptotic approximation of the Radiative Transfer Equation that yields the emerging radiance from a semi-infinite particle cloud. The major source of error in the magnitude of Tg+p and εp could come from particle scattering. Through the method of embedded invariance an expression was developed to estimate the lowering effect of particle size and volume fraction on the saturation of the 4.56-4.7 μm CO2 emission region. An iterative procedure for correcting the values of the gas-particle temperature and particle emissivity was applied to the datasets from the two industrial tests. Results from the measurement campaigns with the infrared sensor prototype at two full-scale furnaces are presented. A proof-of-concept test at a coal-fired boiler for electricity production was followed by more extensive measurements at a Basic Oxygen Furnace (BOF) for steelmaking. The second test provided temperature and particle emissivity profiles for eight heats, which highlighted the simplicity of the technique in obtaining in-situ measurements for modeling studies. Through the analysis of the particle emissivity profile in the BOF and the definition of a new variable –the minimum carbon time– a novel end-point strategy to stop the injection of high-purity oxygen during low-carbon heats in BOF converters was proposed.

A novel technique for measuring gas temperature and spectral particle emissivity in high-temperature gas-particle streams is presented. The main application of this optical sensor is to improve the process control of batch unit operations, such as steelmaking furnaces. The spectral emission profile of CO and CO2 and the continuous particle emission in the 3.5 to 5 μm wavelength region was recorded and analyzed in real time with a low-resolution passive sensor. The sensor consisted of light collecting optics, a dispersion element (grating spectrometer) and a 64-pixel pyroelectric array. Wavelength and radiance calibrations were performed. The temperature of the gas-particle medium (Tg+p) followed from the least-squares minimization of the difference between the measured radiance in the 4.56-4.7 μm region –which saturates due to the large CO2 concentrations and path lengths in industrial furnaces– and the corresponding blackbody radiance. Particle emissivity (εp) was calculated at 3.95 μm from an asymptotic approximation of the Radiative Transfer Equation that yields the emerging radiance from a semi-infinite particle cloud. The major source of error in the magnitude of Tg+p and εp could come from particle scattering. Through the method of embedded invariance an expression was developed to estimate the lowering effect of particle size and volume fraction on the saturation of the 4.56-4.7 μm CO2 emission region. An iterative procedure for correcting the values of the gas-particle temperature and particle emissivity was applied to the datasets from the two industrial tests. Results from the measurement campaigns with the infrared sensor prototype at two full-scale furnaces are presented. A proof-of-concept test at a coal-fired boiler for electricity production was followed by more extensive measurements at a Basic Oxygen Furnace (BOF) for steelmaking. The second test provided temperature and particle emissivity profiles for eight heats, which highlighted the simplicity of the technique in obtaining in-situ measurements for modeling studies. Through the analysis of the particle emissivity profile in the BOF and the definition of a new variable –the minimum carbon time– a novel end-point strategy to stop the injection of high-purity oxygen during low-carbon heats in BOF converters was proposed.

L’objet de la présente étude est le développement, l’application et la diffusion de la technologie associée à divers types d’alliages de cuivre, en particulier l’alliage du plomb-bronze, en Grèce ancienne, dans ses colonies, ainsi qu’en Étrurie. Le plomb-bronze est un mélange de diverses proportions d’étain, de cuivre et de plomb. Le consensus général chez les archéométallurgistes est que le plomb-bronze n’était pas communément utilisé en Grèce avant la période hellénistique; par conséquent, cet alliage a reçu très peu d’attention dans les documents d’archéologie. Cependant, les analyses métallographiques ont prouvé que les objets composés de plomb ajouté au bronze ont connu une distribution étendue. Ces analyses ont aussi permis de différencier la composition des alliages utilisés dans la fabrication de divers types de bronzes, une preuve tangible que les métallurgistes faisaient la distinction entre les propriétés du bronze d’étain et celles du plomb-bronze. La connaissance de leurs différentes caractéristiques de travail permettait aux travailleurs du bronze de choisir, dans bien des cas, l’alliage approprié pour une utilisation particulière. L’influence des pratiques métallurgiques du Proche-Orient a produit des variations tant dans les formes artistiques que dans les compositions des alliages de bronze grecs durant les périodes géométrique tardive et orientalisante. L’utilisation du plomb-bronze dans des types particuliers d’objets coulés montre une tendance à la hausse à partir de la période orientalisante, culminant dans la période hellénistique tardive, lorsque le bronze à teneur élevée en plomb est devenu un alliage commun. La présente étude analyse les données métallographiques de la catégorie des objets coulés en bronze et en plomb-bronze. Elle démontre que, bien que l’utilisation du plomb-bronze n’était pas aussi commune que celle du bronze d’étain, il s’agissait néanmoins d’un mélange important d’anciennes pratiques métallurgiques. Les ères couvertes sont comprises entre les périodes géométrique et hellénistique. / The subject of this study is the development, application and diffusion of the technology of various types of copper alloys, particularly that of leaded bronze, in ancient Greece, its colonies, and in Etruria. Leaded bronze is a mixture of tin, copper and lead in various proportions. The general consensus among archaeometallurgists is that leaded bronze was not commonly used in Greece until the Hellenistic period, and thus this alloy has not received very much attention in archaeological literature. However, metallographic analyses demonstrate that objects composed of leaded bronze had a wide distribution. The analyses also show differentiation in the composition of alloys that were used in the manufacture of various types of bronzes, a tangible indication that metalworkers distinguished between the properties of both tin bronze and leaded bronze. The knowledge of their different working characteristics is what enabled a bronzeworker to choose, in many cases, the appropriate alloy for a specific application. The influence of Near Eastern metallurgical practices produced variations in both the artistic forms as well as alloy compositions of Greek bronzes during the Late Geometric and Orientalizing periods. The use of leaded bronze for particular types of cast objects shows an increasing tendency from the Orientalizing period onwards, culminating in the late Hellenistic period when high-lead bronze became a common alloy. This study analyzes the metallographic data of specific categories of bronze and leaded bronze cast objects, and it will demonstrate that although the use of leaded bronze was not as prevalent as that of tin bronze, it was nevertheless a significant adjunct of ancient metallurgical practices. The periods surveyed range from the Geometric to the Hellenistic periods.

146f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-03T13:18:57Z No. of bitstreams: 1 Tese Hadla S Ferreira.pdf: 1335067 bytes, checksum: d1c32c23138aa8d7c8145b340260a496 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-04-23T15:10:36Z (GMT) No. of bitstreams: 1 Tese Hadla S Ferreira.pdf: 1335067 bytes, checksum: d1c32c23138aa8d7c8145b340260a496 (MD5) / Made available in DSpace on 2013-04-23T15:10:36Z (GMT). No. of bitstreams: 1 Tese Hadla S Ferreira.pdf: 1335067 bytes, checksum: d1c32c23138aa8d7c8145b340260a496 (MD5) Previous issue date: 2009 / CAPES / Neste trabalho, foram desenvolvidos métodos para determinação de cádmio e chumbo em amostras ambientais e antimônio e arsênio em amostras de alimentos, utilizando técnicas de espectrometria atômica. A determinação do cádmio e do chumbo foi realizada através de um sistema de injeção em fluxo acoplado a técnica TS FF AAS. Os íons de cádmio (II) e chumbo (II) foram retidos em uma mini-coluna de Amberlite de XAD – 7 impregnada com ditizona. O planejamento Box- Behnken foi empregado para determinação das condições ótimas da etapa de concentração do chumbo e do cádmio. Os limites de detecção foram de 0,012 e 0,34 μg L-1 para cádmio e chumbo, respectivamente. O método foi aplicado em amostras de resíduos de refinaria de petróleo. A exatidão foi confirmada por análise da CRM NIST 1643d. Foi também desenvolvido um método para determinação de espécies tóxicas de arsênio e antimônio em amostras de alho e cogumelos, respectivamente por HG AFS. A determinação das espécies (III) e (V) de arsênio e antimônio foram baseadas na eficiência de geração de hidreto empregando NaBH4, com e sem uma prévia redução com KI, usando equações proporcionais correspondentes para as duas condições de medida. Os analitos foram extraídas com ácido sulfúrico nas condições de 1,0 e 0,5 mol L-1 para arsênio e antimônio, respectivamente. Com o método desenvolvido obteve-se limites de detecção de 0,6, 1,1, 0,84 e 1,4 ng g-1 para Sb(III), Sb(V), As(III) e As(V), respectivamente. A exatidão do método foi confirmada através de testes de adição e recuperação das espécies bem como, um material de referência certificado NIST 1573a. Um método para determinação de arsênio total em vinho também foi desenvolvido. O arsênio foi determinado por FI-HG AAS com um sistema de atomização eletrotérmica. O planejamento Box-Behnken foi utilizado na determinação das condições ótimas para geração de hidreto. Com método proposto obteve um limite de detecção de 0,06 μg L-1 e foi aplicado em 20 amostras de vinhos comercializadas do Brasil. / Salvador

Submitted by ANA KARLA PEREIRA RODRIGUES (anakarla_@hotmail.com) on 2017-07-31T12:10:23Z No. of bitstreams: 1 arquivototal.pdf: 5468289 bytes, checksum: dc45efa53e8cc6251d00164b611309f9 (MD5) / Made available in DSpace on 2017-07-31T12:10:23Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 5468289 bytes, checksum: dc45efa53e8cc6251d00164b611309f9 (MD5) Previous issue date: 2016-05-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In the last decade, the extraction magnetic solid phase (MSPE) has been intense study target in Analytical Chemistry, mainly because of its potential application in sample preparation. Recently, with the development motivation automatic analytical methods, this technique has been combined with flow systems. However, the synergistic integration of MSPE with these systems is still a challenge, especially when it involves the handling of viscous matrices. In this perspective, this thesis proposes the development of an effective automated method to perform the MSPE in aqueous and oily matrices. For be applied as magnetic adsorbent nanoparticles of Fe3O4 coated with alumina and functionalized with sodium dodecyl sulfate (SDS) and 1-(2-pyridylazo)-2-naphthol (PAN) were synthesized. The nanoparticles were characterized by diffraction analysis X-ray and scanning electron microscopy, where it was confirmed that the method used to obtain the particles was adequate. Secondly, the automatic system to run the MSPE was developed. To this end an extraction chamber was made of Teflon with a quartz window on the side, where all steps of MSPE was performed without the need for any auxiliary apparatus for immobilizing the adsorbent. For generating the magnetic field in the extraction chamber, a robotic device has been developed. After these steps, the applicability of the method was demonstrated in the extraction and preconcentration of Cd and Pb in drinking water samples and Cd in edible oils, using as detection atomic absorption spectrometry graphite furnace. Factors affecting MSPE, such as pH, the amount of adsorbent, the type and concentration of the eluent and the elution time were studied. In the best experimental conditions to the sample water, the detection limit was 0.004, and 0.043 ug L-1 for Cd and Pb, respectively. Even in this array, relative standard deviations less than 3.5% were achieved with a 15-fold enrichment factor for both analytes. In the case of determination of Cd in edible oils, detection limit (0.006 ug L-1) and standard deviation (< 3.3%) was obtained satisfactorily with a 9-fold enrichment factor. Interfering studies have been performed successfully for the two determinations, not revealing significant percentage interference in determinations. The developed automatic method is simple and robust since it does not require immobilization of the adsorbent, and was successfully applied in the determination of Cd and Pb in drinking water samples and Cd in edible oils. / Na última década, a extração em fase sólida magnética (MSPE) tem sido alvo de intenso estudo na Química Analítica, principalmente em virtude do seu potencial de aplicação no preparo de amostras. Recentemente, tendo como motivação o desenvolvimento de métodos analíticos automáticos, essa técnica vem sendo combinada aos sistemas em fluxo. Contudo, a integração sinérgica da MSPE com esses sistemas ainda é um desafio, principalmente quando envolve a manipulação de matrizes viscosas. Nessa perspectiva, a presente tese propõe o desenvolvimento de um eficiente método automático para realização da MSPE em matrizes aquosas e oleosas. Para serem aplicadas como adsorvente magnético foram sintetizadas nanopartículas de Fe3O4 revestidas com alumina e funcionalizadas com dodecil sulfato de sódio (SDS) e 1-(2-piridilazo)-2-naftol (PAN). As nanopartículas foram caracterizadas através da análise de difratometria de raios-X e da microscopia eletrônica de varredura, onde confirmou-se que o método empregado para obtenção das partículas foi adequado. Num segundo momento, o sistema automático para executar a MSPE foi desenvolvido. Para isso, uma câmara de extração foi confeccionada em Teflon, com uma janela de quartzo na lateral, onde todos os passos da MSPE foram realizados sem a necessidade de qualquer aparato auxiliar para imobilizar o adsorvente. Para geração do campo magnético, na câmara de extração, um dispositivo robótico foi desenvolvido. Depois de estabelecida essas etapas, a aplicabilidade do método foi demonstrada na extração e preconcentração de Cd e Pb em amostras de água de abastecimento e de Cd em óleos comestíveis, empregando como detecção a espectrometria de absorção atômica em forno de grafite. Fatores que afetam a MSPE, tais como o pH, a quantidade de adsorvente, o tipo e a concentração do eluente e o tempo de eluição foram estudados. Nas melhores condições experimentais, para a amostra água, o limite de detecção foi 0,004 e 0,043 μg L-1 para o Cd e o Pb, respectivamente. Ainda nessa matriz, desvios padrão relativos menores que 3,5 % foram alcançados com um fator de enriquecimento de 15 vezes para ambos os analitos. No caso da determinação de Cd em óleos comestíveis, limite de detecção (0,006 μg L-1) e desvio padrão relativo (< 3,3 %) satisfatório foi obtido com um fator de enriquecimento de 9 vezes. Os estudos de interferentes foram realizados com êxito para as duas determinações, não revelando interferência percentual significativa nas determinações. O método automático desenvolvido é simples e robusto, uma vez que não requer a imobilização do adsorvente, e foi aplicado com sucesso na determinação de Cd e Pb em amostras de água de abastecimento e de Cd em óleos comestíveis.