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.

Made available in DSpace on 2014-07-29T15:18:25Z (GMT). No. of bitstreams: 1 dissertacao marcus vinicius mendes.pdf: 2369089 bytes, checksum: 841841ae88caf7c6c9adb67b65e533c5 (MD5) Previous issue date: 2009-10-06 / The durability of reinforced concrete structures is damaged by the degrading action of the penetration of substances in the form of gases, vapors and liquids through the pores and cracks. It is known that water both in its pure form or containing dissolved ions such as chloride, sulphate, carbon dioxide or oxygen ions, can compromise the durability of concrete structures. In reinforced concrete structures at the marine environment, for example, the towers of wind power plants, this degradation can be more intense and accelerated. Thus, in the present study were analyzed concretes with different mineral additions (silica fume, blast furnace slag) and water / binder ratios (0.35, 0.45 and 0.55), with the objective to verify if the inside and cover thickness of concrete have some effect on the mechanisms of transport and also the effect of carbonation (only for concrete with w/b equal to 0.55) in the surface layer of concrete is important enough to make dificult the entry of aggressive agents in concrete. For this, the following tests to evaluate the mass transport in concrete were performed: capillary water absorption (NBR 9779:1995), water penetration under pressure (NBR 10787:1994), air permeability (method Figg), penetrability of chloride ion (ASTM C 1202: 2009), non-steadystate migration test (NT BUILD 492:1999). As a result, it was found that the mineral addition used generally provided an improvement in front of the concrete mechanisms of mass transport. In one of the properties, namely the diffusion coefficient (non-steady-state migration) of concrete with the use of silica fume and blast furnace slag, this has been reduced dramatically, around 11 times for the concrete with w/b equal to 0.55, when it is compared with concrete without mineral addition. It was observed that the inner region of concrete behaved better, in an unexpected way, than concrete cover region for some properties (capillary absorption, water penetration under pressure, penetration of chloride ions). From this conclusion, it can be said that the inner part of concrete is composed of transition zones (aggregated interface / mortar) exposed to facilitate the entry of fluids, gases and ions. About the effect of carbonation, this affected the capillary absorption and air permeability. The results led to explain that the clogging of the pores resulting from the product of carbonation (CaCO3), promoted the refinement of the pores, thus increasing capillary force and, consequently, increasing the capillary absorption. However, for air permeability this effect has damaged the passage of air through the surface layer. Finally, it is important noting that significant correlations were found among tests that evaluated the mechanisms of mass transport, namely, penetration of chloride ions and capillary absorption, diffusion coefficient (non-steady-state migration) and capillary absorption, permeability air and water penetration under pressure, penetration of chloride ions and the diffusion coefficient. / A durabilidade das estruturas de concreto armado é prejudicada pela ação deteriorante da penetração de substâncias na forma de gases, vapores e líquidos através de poros e fissuras. Sabe-se que a água, tanto no seu estado puro ou com íons dissolvidos, como os cloretos, sulfato, dióxido de carbono ou oxigênio, pode comprometer a durabilidade das estruturas de concreto. Em estruturas de concreto armado localizadas em ambiente marítimo como, por exemplo, as torres de energia eólica, essa deterioração pode ser mais intensa e acelerada. Diante disso, no presente trabalho foram analisados concretos com diferentes adições minerais (sílica ativa e escória de alto-forno) e relações água/aglomerante (0,35; 0,45 e 0,55), tendo como objetivo principal verificar se a parte interna e o cobrimento do concreto exercem algum efeito nos mecanismos de transporte e, se o efeito da carbonatação (somente para concretos de relação a/g igual a 0,55) na camada superficial do concreto é relevante a ponto de dificultar a entrada de agentes agressivos no concreto. Para isso, foram realizados os seguintes ensaios para avaliar o transporte de massa no concreto: absorção de água por capilaridade (NBR 9779:1995), penetração de água sob pressão (NBR 10787:1994), permeabilidade ao ar (método de Figg), penetrabilidade de cloretos (ASTM C 1202: 2009), ensaio de migração em regime não estacionário (NT BUILD 492:1999). Como resultado constatou-se que as adições minerais empregadas propiciaram de maneira geral uma melhoria dos concretos frente aos mecanismos de transporte de massa. Em uma das propriedades avaliadas, a saber, o coeficiente de difusão (migração regime não estacionário) dos concretos com o emprego de sílica ativa e escória de alto-forno, esse foi reduzido drasticamente, em torno de 11 vezes para os concretos com relação a/ag igual a 0,55, quando comparado com os concretos sem adição mineral. Quanto à região do concreto, notou-se para algumas propriedades (absorção capilar, penetração de água sob pressão, penetrabilidade de cloretos) que a região interna comportou-se melhor, de maneira inesperada, que a região do cobrimento. Diante dessa conclusão, criou-se uma hipótese para tal comportamento que consistiu em afirmar que a parte interna é composta por zonas de transição (interface agregado/pasta) expostas que facilitam a entrada de fluidos, gases e íons. Já com relação ao efeito da carbonatação, esta afetou a absorção capilar e a permeabilidade ao ar. Os resultados levaram a explicar que a colmatação dos poros, advindos do produto (CaCO3) da carbonatação promoveu o refinamento dos poros, aumentando, assim, a força capilar e, conseqüentemente, o aumento da absorção capilar. No entanto, para permeabilidade ao ar esse efeito dificultou a passagem de ar através da camada superficial. Por último, cabe destacar, que correlações importantes foram obtidas entre os ensaios que avaliaram os mecanismos de transporte de massa, a saber, penetrabilidade de cloretos e absorção capilar, coeficiente de difusão (migração regime não estacionário) e absorção capilar, permeabilidade ao ar e penetração de água sob pressão, penetrabilidade de cloreto e coeficiente de difusão.

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.<p><p>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.<p><p>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.<p><p>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.<p><p><p>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. <p><p>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.<p><p>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. <p><p>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.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

The topic of this work is the monitoring of the effect of zinc on the hydration process in Portland mixed cement (specifically with the addition of finely ground granulated blast-furnace slag, high temperature fly ash and fluidized bed combustion filter ash). How much zinc and at what time it remains in the pore solution during hydration. Activation energy of a mixture of cement with zinc in the form of soluble salts (Zn(NO3)2.6H2O and ZnCl2) and insoluble oxide (ZnO) by isothermal calorimetry was also investigated. The XRF method has shown composition during hydration. The zinc retardation effect was investigated by isothermal calorimetry and activation energy was calculated using this method. The XRF and ICP-OES methods were used to measure the zinc content of the pore solution. And the amount of portlandite was monitored by the DTA and XRF method.

This work is devoted to study the influence of the composition on mechanical properties of high performance concret based on portland cement. 29 samples of high performance concrete (HPC) warying in composition were prepared. The constituents used for HPC preparation were: cement Aalborg White, silica fume, finelly ground blast furnace slag, finelly ground silica, calcinated bauxite and polycarboxylate based superplasticizer. The mechanical parameters (flexural and compressive strength) of the samples were observed after 7 and 28 days of moist curing. Compressive strength values after 28 days were in the range of 92 to 194 MPa and the flexural strength values were in the range of 7 to 23 MPa (without using of fiber reinforcement). The graphs showing mechanical parameters depending on the mixture composition were constructed and consequently evaluated.

This paper discusses different alternatives of more efficient preparation of spheroided graphite cast iron production. Secondary metallurgy and chemical heating technology are used to recast cast iron fused in copula furnace. The work applies the known physical-chemical rules used in the production of quality spheroided graphite cast iron in regular production conditions. Based on the previous developments, the aim was to prepare implementation of verified secondary metallurgy processes in adjusted casting ladle. The casting ladle was adjusted in order to allow execution of all processes required in order for the relevant standards and material lists requirements to be met in respect to spheroided graphite cast iron quality. Comments regarding the trends in ferroalloy metallurgy and related marketing approach of the company. The work is concluded by a summary of advantages brought in by the new approaches compared to the traditional ones from the economical as well as environmental perspective.

This work thoroughly analyzes a previously created computational model for predicting characteristic properties of the combustion process in an experimental combustion chamber. Any found shortcomings of the original model are removed and the model is further improved prior to its application on 11 real cases of combustion tests performed at various conditions and with various fuels. Data provided by the model are confronted with the data obtained during the combustion tests and the model accuracy is evaluated, based on local heat flux along the length of the combustion chamber. Finally, the overall usefulness of the model is determined by the means of evaluating the acquired accuracy values, and further possibilities of model improvement and use are presented.

Civil engineering development is connected with the application of new construction methods and the development of new building materials. Concrete, as one of the basic building materials, is part of this development. A major turning point in the development of concrete and its properties occurred with the use of new, more efficient plasticizing additives. This allowed to produce concrete with lower water cement ratio, while increasing the strength of concrete. Gradually, the compressive strength of concrete boundary has moved by several levels, when there are currently commonly used concrete with strength of about 100 N/mm2 and with the special methods of concrete production strength range from 250 to 300 N/mm2. A negative aspect of the development of (ultra) high-strength concrete is their energy and economic demands. A characteristic feature of high-strength concrete is a high content of cement and very fine admixtures, especially silica fume. One way to improve the economics of these types of concrete is the application of cheaper admixture based on industrial waste. The content of this work is the observation and description of the properties of high-strength concrete and reactive powder concrete, in which the admixtures were based on industrial waste were applied. Part of this work is the comparison of economic parameters for individual types of concrete.

The theme of this work is to monitor the effect of zinc on the properties of blended Portland cements. Zinc was tested in the form of two-soluble salts: Zn(NO3)22 H2O and ZnCl2 and a very slightly soluble compound ZnO. Blended cements were prepared by partial replacement with finely ground granulated blast furnace slag, high-temperature and fluidized bed combustion filter fly ash. Flow properties were studied on the prepared pastes. Impact on hydration reactions was examined by using of isothermal and isoperibolic calorimetry. Flexural and compressive strength were measured as mechanical properties of the prepared test specimens. The phase composition of the prepared composites and incorporation of zinc ions in the cement matrix via leaching tests and FTIR analyzes were also studied. Microstructure development of cement samples was tested by SEM analysis with EDS. Influence on ecotoxicity was also measured.