Neste trabalho é descrito um procedimento para a determinação quantitativa da espessura e composição química de filmes finos, por fluorescência de raios X por dispersão de comprimento de onda (WDXRFS), utilizando-se o método de Parâmetros Fundamentais (FP). Este método foi validado dentro dos padrões de garantia de qualidade e aplicado as amostras de Al, Cr, TiO2, Ni, ZrO2 (monocamada) e Ni/Cr (duplacamada) sobre vidro; Ni sobre aço inoxidável e zinco metálico e TiO2 sobre ferro metálico (monocamada), as quais foram preparadas por deposição física de vapor (PVD). Os resultados das espessuras foram comparados com os métodos de Absorção (FRX-A) e Retroespalhamento de Rutherford (RBS), demonstrando a eficiência do método de parâmetros fundamentais. As características estruturais das amostras foram analisadas por difração de raios X (DRX) e mostraram que os mesmos não influenciam nas determinações das espessuras. / In this work a procedure is described for thickness and quantitative chemical composition of thin films by wavelength dispersion X-ray fluorescence (WDXRF) using Fundamental Parameters method. This method was validated according to quality assurance standard and applied sample Al, Cr, TiO2, Ni, ZrO2 (single thickness) and Ni/Cr (double thickness) on glass; Ni on steel and metallic zinc and TiO2 on metallic iron (single thickness), all the sample were prepared for physical deposition of vapor (PVD). The thickness had been compared with Absorption (FRX-A) and Rutherford Backscattering Spectrometry (RBS) methods; the result showed good efficiency of the fundamental parameters method. Sample structural characteristics analyzed by X ray diffraction (XRD) showed any influence in the thickness determinations.

O diabetes mellitus é umas das principais endocrinopatias da espécie canina. Esta doença é caracterizada pela deficiência relativa ou absoluta de insulina. A formação da catarata é uma complicação freqüente do cão diabético, resultando em cegueira. A lente do paciente diabético está sujeita ao aumento do estresse oxidativo em razão da dificuldade em regular os níveis glicêmicos gerando hiperglicemia crônica. Os elementos químicos estão envolvidos em diversos processos no organismo. Portanto, alterações como deficiência ou excesso dos elementos químicos podem contribuir para as complicações do diabetes mellitus, incluindo a catarata. A cápsula da lente, importante estrutura na cirurgia de catarata, está associada com uma diminuição da espessura, tornando-se mais fina como o avanço da catarata. O objetivo deste estudo foi determinar, por meio do uso da fluorescência de raios X (XRF), a concentração dos elementos químicos cálcio, ferro, cobre e zinco e analisar a topografia dos elementos traços ferro, cobre e zinco. Por meio dos mapas de distribuição determinou-se as regiões de intensa atuação dos elementos constituintes e traços, e seu papel efetivo para a lesão. E por meio da microscopia de força atômica (MFA) determinar as propriedades biomecânicas associadas à catarata em cães. A fluorescência de raios X mostrou-se eficiente para a determinação da concentração elementar de cálcio, ferro, cobre e zinco em cataratas de cães portadores de diabetes mellitus. As análises quantitativas mostraram um aumento na concentração e redução na concentração de ferro e cobre nas lentes de cães diabéticos. Estes resultados concordam com hipóteses discutidas na literatura. A microscopia de força atômica proporcionou medidas elasticidade rápidas e precisas em amostras de cápsula anterior da lente de cães, com mínima preparação da amostra. Os valores de elasticidade local apresentaram-se ligeiramente superiores para lentes diabéticas. / Diabetes mellitus is one of the principal endocrinopathies in canine. The disease is characterized by absolute or relative deficiency of insulin. The formation of cataract is frequent complication in diabetic dogs, leading to blindness. The lens of diabetic patient is subjected to increased oxidative stress due to the difficulty in regulating blood glucose levels causing chronic hyperglycemia. The chemical elements are involved in several functions in the organism. Therefore, alterations like deficiency or excess of chemical elements may contribute to the complications of diabetes mellitus including cataract. The lens capsule, an important structure of cataract surgery is associated to a decrease in thickness, becoming thinner with the advance of the cataract. The objective of this work was to determine, through the use of X ray fluorescence (XRF), the concentration of chemical elements such as calcium, iron, cooper and zinc and analyze the topography of the trace elements iron, cooper and zinc. By the means of elementary distribution maps we could determine the regions of the intense action of the constituent elements and trace and its effective role in relation to the lesion. By means of atomic force microcopy (AFM), we could determine the biochemical properties associated to the cataract in dogs. X ray fluorescence showed efficient for the determination of the elementary concentration of calcium, iron, cooper and zinc in cataracts in dogs carrying diabetes mellitus. Quantitative analysis showed an increase in calcium and a reduction in iron and copper concentration in lenses of diabetic animals. These results are in accordance to the hypothesis discussed in the literature. The atomic force microscopy provided measures of rapid and accurate elasticity in samples of anterior capsules of lenses in dogs, with minimum preparation of samples. The values of local elasticity showed slightly superior for diabetic lenses.

A queima de biomassa em fornos de pizzaria se constitui como importante fonte de poluição do ar. Entre outros tipos de poluentes emitidos, o material particulado finoMP2,5 se destaca como o mais agressivo à saúde humana, além de poder interferir no balanço radiativo global. Objetiva-se, desta forma, através de estudo de caso em três pizzarias na cidade de São Paulo, quantificar e caracterizar o MP2,5 emitido pela queima da biomassa na área interna (indoor) e externa (junto á chaminé). Dentre as três pizzarias, duas fazem uso da lenha de eucalipto e a outra faz uso do briquete, formado a partir da compactação de pedaços de biomassa, serragem, bagaço e outros resíduos madeireiros. As amostras foram coletadas utilizando-se o amostrador Minivol. A análise do material foi realizada por meio de técnicas complementares: gravimetria (para a concentração em massa), refletância (para a concentração de black carbon), fluorescência de raios-X (para a concentração elementar) e utilização do microscópio eletrônico de varredura (MEV) (para identificar a morfologia do material particulado). Além disso, foram feitas inferências na saúde do trabalhador quanto á exposição ao MP2,5, e por fim foi estimada as emissões de MP2,5 e black carbon dado o elevado número de pizzarias existentes na cidade de São Paulo. Os resultados apresentaram concentrações médias elevadas de MP2,5, 6171,14 g/m3 no ambiente externo, e 68,24 g/m3 no ambiente interno para as três pizzarias. A queima do briquete apresentou menores concentrações para MP2,5. Os elementos químicos potássio, cloro e enxofre foram os mais representativos em termos de concentração. Os resultados para o MEV revelaram partículas com morfologia esférica individual, conglomerado de partículas esféricas, partículas achatadas com o formato de fibras, sobreposição de camadas e aglomerados de partículas com aspecto esponjoso. Embora no Brasil não exista padrão de exposição para o MP2,5 em ambiente interno, quando comparado com o padrão de exposição da Alemanha, as concentrações obtidas nas três pizzarias são superiores. Concentrações em massa de elementos prejudiciais à saúde como o cromo e zinco se mostraram demasiadamente elevadas. Os fatores de emissão para o MP2,5 e black carbon provenientes da queima da lenha foram 0,38g/kg e 0,23g/kg, respectivamente; e para o briquete 1,04g/kg e 0,37g/kg respectivamente. As emissões de MP2,5 e black carbon foram de 0,958t/ano e 0,340t/ano para a queima do briquete e 116,736t/ano e 70,656t/ano para a queima da lenha / The burning of biomass in pizza ovens constitutes itself as an important source of air pollution. Compared with other types of pollutants emitted, the fine particulate matter PM2,5 highlights itself as one of the most aggressive to human health, besides the power to interfere with global radiative balance. Therefore, through the study of three São Paulo pizzerias, the quantification and characterization of PM2,5 emitted by the burning of biomass within internal areas and external (where chimney´s were present). Among the three pizzerias, two used eucalyptus timber logs while the remaining other used wooden briquettes; formed by the compression of biomass: chips and shavings and other wood residue. Samples were collected using Minivol. The analysis of the material was completed via complementary techniques: gravimetrically (to establish mass concentration) Reflectance (to establish black carbon concentration) X-ray fluorescence (to establish element concentration) and the use of an electro-microscopic sweep (SEM) (to indentify the morphology of the particulate matter). Beyond this, inferences were made about the health of workers exposed to PM2,5, by way of estimated emissions of PM2,5 due to the elevated number of pizzerias in São Paulo. The results from the three pizzerias revealed elevated average concentrations of PM2,5, 6171,14 g/m3 in external areas and 68,24 g/m3 in internal areas. The burning of briquette revealed lower concentrations of PM2,5. The chemical elements: potassium, chlorine and sulfur were the most represented in terms of concentration. The results of the SEM (electro-microscopic sweep) revealed particles with an individual and spherical morphology, the conglomeration of spherical particles, flattened particles in the formation of fibers, the overlapping of layers and the clustering of particles with sponge-like qualities. Although in Brazil there are no existing parameters for PM2,5 exposure in internal areas, when compared with the established exposure parameters in Germany, the concentrations obtained within the three pizzerias exceeded those parameters. Concentration en masse of elements dangerous to health such as chrome and zinc were shown to be excessive. The rate of emissions of PM2,5 and black carbon due to the burning of logs were 0,38g/kg and 0,23g/kg, respectively; and for briquettes were 1,04g/kg and 0,37g/kg, respectively. The emissions of PM2,5 and black carbon were from 0,958t/year to 0,340t/year in the burning of briquettes and from 116,736t/year to 70,656t/year in the burning of timber logs

O resíduo estudado neste trabalho é originado do processo de obtenção de alumínio metálico, de grande interesse no Brasil pelo fato do país ser detentor de algumas das maiores reservas do mineral bauxita no mundo, utilizado como fonte de alumínio. Tendo como estratégia a geração de resíduo zero, colaborando para as tecnologias ambientalmente amigáveis, este trabalho estuda a incorporação de um resíduo resultante da recuperação de alumínio presente na escória gerada durante o processo de produção primária do alumínio metálico, por plasma térmico. Utilizando-se o diagrama de equilíbrio de fases do sistema Al2O3-CaO-SiO2, fez-se a adequação das composições visando a incorporação de resíduo no produto cerâmico sem alterar as características de processamento do material. A obtenção de vidros e de fritas vitrocerâmicas com o resíduo borra branca foi realizada fazendo-se a fusão das composições calculadas e, para os vitrocerâmicos, tratamento térmico posterior de devitrificação. Os produtos obtidos foram caracterizados utilizando-se técnicas de análise tais como difração de raios X (DRX), microscopia eletrônica de varredura (MEV) e espectroscopia do infravermelho (FTIR). Foi possível obter material vitrocerâmico com até 30% de resíduo de alumínio, após a fusão a 1300°C e devitrificação a 900°C. Em adição, o resíduo demonstrou ser um promissor material auxiliar na formação de fases cristalinas em baixos tempos de tratamento térmico. / This work studies the residue obtained from the process of aluminum metal extraction activities, a great interest process, because of Brazil own some of the biggest bauxite mineral reserves in all the world. As a useful choice for no residue generation, and a support for environmentally friendly technologies, this work studies the white dross residue (WDR), from the process of aluminum metal reduction by thermal plasma. The phase equilibrium diagram of Al2O3-Ca O-SiO2 system was used to calculate the compositions. The WDR were incorporated in a ceramic product without modifying its principal characteristics. The fusion and devitrification treatments were studied. XRD (X-ray diffractometry), SEM (scanning electron microscopy) and FTIR (transformed Fourier infrared) were used to investigate the glass and glassceramic samples. These techniques showed that is possible to get glassceramic with up to 30 mass% of WDR after molten at 1300 deg C and annealed at 900 deg C. In addition, the WDR showed to be a promising material in attainment of crystalline phases in less times of heat treatment for annealing.

[pt] Os compostos de enxofre estão presentes em todos os derivados de petróleo bruto. Para o meio ambiente, dois poluentes resultantes da queima do óleo diesel são considerados críticos, o material particulado (MP) e os óxidos de nitrogênio. Sendo que o primeiro tem relação direta com o teor de enxofre no óleo diesel e a presença do segundo nos gases de escapamento tem relação primordial com o projeto de motor. Daí a importância do monitoramento do teor de enxofre em óleo diesel, cuja qualidade e a rastreabilidade de medição foi verificada em seis laboratórios do Rio de Janeiro através de uma participação em um Programa de Comparação Interlaboratorial. Houve a necessidade de enquadramento da técnica de medição de enxofre por fluorescência de raios-x (FRX) baseado na norma ASTM D 2622-98 em cumprimento aos requisitos da ABNT ISO/IEC 17025, a qual especifica a competência para a realização de ensaios e/ou calibrações. O objetivo deste trabalho foi realizar uma análise metrológica do ensaio de determinação do teor de enxofre em óleo diesel por fluorescência de raios-x. Foram utilizados como parâmetros de desempenho, a faixa de trabalho, a linearidade, o limite de detecção e de quantificação, a exatidão, a repetitividade, a reprodutibilidade e a incerteza de medição. Nesta análise metrológica foi observado que o uso de material de referência certificado e os parâmetros de desempenho no limite de 95,45 por cento de confiança apresentaram resultados compatíveis com a metodologia. Quanto ao desempenho no ensaio de proficiência dos laboratórios participantes, o programa orientou-os na identificação de erros não detectados pelo próprio laboratório, propiciando o aprimoramento das técnicas analíticas, melhoria na qualidade das medições e maior confiabilidade dos resultados obtidos. / [en] Sulfur compounds are among the components of most crude oils and their products. When burning diesel fuel, two main pollutants are discharged into the atmosphere. Particulate matter (PM) is directly related to the amount of the sulfur content in the diesel fuel. Nitrogen oxides in the exhaust gases are a direct function of the engine design and operating conditions. It is therefore important to monitor the sulfur content of the diesel fuel. In this dissertation, its measurement quality and traceability were determined when comparing the results obtained by six laboratories, which are operating in the state of Rio de Janeiro. The x-ray fluorescence (XRF) sulfur measurement technique, as described by the ASTM D2622-98 standard, was used by all the laboratories in this intercomparison program, which was conducted following the ABNT ISO/IEC 17025 standard. The objective of this work is thus to perform a metrological evaluation of the sulfur content in the diesel fuel through the x-ray fluorescence technique. Working range, linearity, resolution, accuracy, repeatability, reproducibility and measurement uncertainty are the parameters used for the performance evaluation, as referred to the 95,45 percent confidence level. The metrological evaluation showed that the use of a certified reference material, together with the performance evaluation parameters, produced results, which were compatible with the used methodology. This intercomparison program also helped the laboratories to identify nonpreviously detected measurement errors, thus improving the measurement quality and reliability in the analytical technique.

Imitation of archeological artifacts or replacing the authentic ones with fake replicates is a universal problem / it is particularly important in Turkey for historical metal objects. Traditionally used visual inspection methods alone are not sufficient for the solution of contemporary problems. In this study, chemical characterization has been used to determine the differences between the authentic and fake objects. The non-destructive analyses were carried out by Portable X-ray Fluorescence Spectrometry (P-XRF). Silver Roman Coins (27 B.C. to 244 A.D.) were the objects handled in this research. In particular the concentrations of Zr, Pt, Pb and Bi were used for differentiation / it has been observed that the concentrations have different trends in the authentic and fake silver coins. In authentic coins the average Pb concentration was found to be 0.77%, while this value was 0.055% for the fake ones. Bi could be determined in 86% of the authentic coins while it could not be detected in any fake coin. It has been generally observed that the silver and copper concentrations could not be utilized in authenticity tests. Another approach was the use of Line Scanning Electron Microscopy-Energy Dispersive X-Ray Fluorescence Spectrometry (LSEM-EDX). Using LSEM-EDX technique, it was observed that the concentration changes near the interface between the matrix and the copper-rich locations exhibits difference behaviors for the authentic and fake objects. This difference is originated by the fact that a newly formed copper amalgam contains copper-rich phases while with extended time concentration changes at interfaces become more gradual or not detectable. Pearson correlation was used in order to elucidate the relations between the element concentrations determined by P-XRF. In order to see whether the authentic and silver fake coins can form separate groups, dendograms have been constructed utilizing SPSS 16.0 software and Euclidian Square Distance method. It has been observed that the authentic and fake coins can be successfully grouped when the proper statistical choices are used. It has been observed that these groups have significant differences using t-test. The selected and used technology is proposed for use by museums and entities keeping archaeological collections in order to prevent forgeries.

Ernst Alexander hat sich sowohl als experimentell als auch theoretisch äußerst fähiger Assistent von Georg von Hevesy im Institut für Physikalische Chemie der Universität Freiburg um die Entwicklung der Röntgenfluoreszenzanalyse verdient gemacht, habilitiert und wurde 1933 kurz nach seiner Ernennung zum Privatdozenten entlassen. Er ging an die Hebräische Universität Jerusalem, wo er das Arbeitsgebiet Experimentalphysik mit einer Institutswerkstatt aufgebaut, wesentliche Beiträge zur Röntgenstrukturanalyse geleistet und als Hochschullehrer fähige Wissenschaftler hervorgebracht hat. Während der kriegerischen Auseinandersetzungen stellte er Ersatzteile erst für die britische und dann für die israelitische Armee her. Ungeachtet seiner In Freiburg und in Jerusalem erbrachten Leistungen waren 1956 Institutsdirektor R. Mecke und der Dekan bei der Beurteilung seines Wiedergutmachungsantrages nicht bereit, ihm einen positiven Verlauf seiner akademischen Laufbahn zu bescheinigen, wenn er in Deutschland seine Arbeit hätte fortsetzen können. / Ernst Alexander was an assistant of George de Hevesy in the institute of physical chemistry of the university in Freiburg. He was a skillful experimenter with broad knowledge. He has done important contributions in the development of x-ray fluorescence analysis and has been qualified to give lectures at the university. In 1933 shortly after his appointment as lecturer he was dismissed. He went to the Hebrew University of Jerusalem, where he founded the laboratory of experimental physics with a workshop, where he dealt with x-ray structural analysis. During the war he produced spare parts for the British and later for the Israeli army. In 1956 he applied for reparation, but the head of the institute, R.Mecke and the dean did not accept that he would obtain a professorship if he must not leave Germany.

ABSTRACT DIFFERENTIATION AND CLASSIFICATION OF COUNTERFEIT AND REAL COINS BY APPLYING STATISTICAL METHODS Tansel, I&ccedil / ten M.Sc, Archaeometry Graduate Program Supervisor : Assist. Prof. Dr. Zeynep Isil Kalaylioglu Co-Supervisor : Prof. Dr. Sahinde Demirci June 2012, 105 pages In this study, forty coins which were obtained from Museum of Anatolian Civilizations (MAC) in Ankara were investigated. Some of those coins were real (twenty two coins) and the remaining ones (eighteen coins) were fake coins. Forty coins were Greek coins which were dated back to middle of the fifth century BCE and reign of Alexander the Great (323 &ndash / 336 BCE). The major aims of this study can be summarized as follow

Studies have been carried out on specific ion-exchange (Dowex 50W-X8 and Dowex 1-X8) and chelation (Chelex-100) resins, in order to determine their physical and chemical characteristics, to understand and explain their limits of function and to optimise their use as substrates in trace metal and speciation measurement by EDXRF. Structural information was obtained by scanning electron microscopy and x-ray microanalysis showing a homogeneous distribution of functional groups and retained ions on both sectioned and whole resins. Particle size experiments performed on Dowex 50W-X8 (38 - 840 µm) showed that this parameter has no effect on the relationship between intensity of fluorescence and concentration or mass of resin. Inter-element effects were not observed in the analysis of multielemental specimens prepared on ion-exchange / chelation media by EDXRF. This indicates that the proposed method has a significant advantage when compared with other methodologies. A theoretical ‘model’, based on the formation of thin films on the surface of the resin beads, has been proposed in order to link and explain the effects observed in these experiments. The use of a batch retention system has shown distinct advantages over using columns in terms of linearity, accuracy, precision, rapidity and simplicity. Parameters such as pH and ionic strength of the solution, concentration of competing ions and volume of the sample have been proven to be critical. The maximum retention capacity has been determined as 3.2, 1.1 and 0.67 mEq/g for Dowex 50W-X8, Dowex 1-X8 and Chelex-100 respectively. The optimum mass of resin for XRF analysis was found to be 0.5 g, for all resins tested. The linear range covered 4 to 5 orders of magnitude. These findings show the potential of the investigated media to overcome instrumental and sample limitations. Based on the physico-chemical information found, methodologies for three different applications of the resins to EDXRF determinations have been developed and their analytical possibilities explored. The multi-elemental determination of metals in sewage sludge digests was achieved by retaining the metals on Dowex 50W-X8 at pH 2 and Chelex-100 at pH 4. Chelex-100 allows quantitative recoveries for Cu and Zn. A wider range of elements was determined on Dowex 50W-X8, although with poorer recoveries (60 - 90%). The limits of detection were 10 - 21 µg when Dowex 50W-X8 was used and 8 - 49 µg for Chelex-100. The method was validated by the analysis of a certified material. The determination of Kβ/Kα intensity ratios for Cr and Mn species and its potential as a tool for direct elemental speciation has also been studied. A difference in Kβ/Kα between the oxidation states of the analytes was only observed during the analysis of solutions of the metal species by EDXRF at the 98% level of confidence. Finally, the speciation and preconcentration of Cr(III) and Cr(VI) in waters has been performed by retention on Dowex 50W-X8 and Dowex 1-X8 followed by EDXRF determination. Efficient recoveries and preconcentration factors of up to 500 were achieved, leading to limits of detection of 30 µg/L for Cr(VI) and 40 µg/L for Cr(III). This method is simple, fast and inexpensive, allowing quantitative recoveries in the speciation of chromium in waste waters.

A proposta do referente estudo foi medir a espessura do depósito de um metal em outro metal base, ou seja, utilizar o processo eletroquímico de Galvanoplastia ou eletrodeposição deste metal, por meio da técnica de fluorescência de raios X (XRF). O uso desta técnica justificou-se pelo interesse em reduzir os custos excessivos durante o processo eletroquímico, bem como, minimizar as possíveis margens de erros para obter resultados satisfatórios nas medidas. Neste trabalho, incluíram-se as medidas da espessura do Níquel (Ni) e análises da intensidade de radiação incidentes e a radiação atenuante, em função da espessura dos elementos Cromo (Cr) e Zinco (Zn), considerando como metal base o elemento Ferro (Fe). Em decorrência disso, em todos os casos foram simulados os processos de deposição do metal onde foram incluídos os resultados de absorção de raios X, além de desprezar a influência de outros fatores como a temperatura, o pH, o tratamento de superfície, entre outros, os quais são necessários para considerar em cada caso. / The proposal concerning the study was to measure the thickness of the deposit of a basemetal into another metal, ie, using the electrochemical processes of the electroplating orelectrodeposition of this metal, through the technique of X-ray fluorescence (XRF). The use of this technique was justified by the interest in reducing the excessive costs during the electrochemical process, as well as minimize the possible margins of error to obtain satisfactory results in the measures. In this paper, we include measures of the thickness of the nickel (Ni) and analysis of radiation mitigation and radiation incidents, according to the thickness of the elements Chromium (Cr) and zinc (Zn), taking as base metal element iron (Fe). As a result, in all cases were simulated processes of metal deposition which included the results of X-ray absorption, and neglect the influence of other factors such as temperature, pH, surface treatment, among others, which are necessary to consider in each case.