Dissertations / Theses on the topic 'Energy dispersive spectrometry'

Thesis (M.S. in Applied Physics) Naval Postgraduate School, December 1999.
"December 1999". Thesis advisor(s): Alan G. Fox, James Luscombe. Includes bibliographical references (p. 69-70). Also available online.

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.

PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO
A determinação de diferentes níveis de silício e alumínio em petróleo é importante porque pequenas quantidades destes elementos podem produzir efeitos adversos nas refinarias devido à corrosão de equipamento ou afetar a qualidade dos produtos refinados. A espectrometria de fluorescência de raios-X por dispersão de energia (EDXRF) foi utilizada para desenvolver um método para a determinação de Si e Al em petróleo, onde estes elementos se encontram principalmente sob a forma de partículas sólidas de aluminossilicatos dispersas na amostra. Uma vez que os analitos não puderam ser determinados sem interferência diretamente no óleo, a fusão das amostras de petróleo foi realizada utilizando tetraborato de lítio. Em seguida, as amostras fundidas foram colocadas no centro de papéis de filtro de 10 mm de diâmetro, que foi colocado entre duas folhas de filme de polipropileno, para então ser fixado à cubeta para as medições no instrumento. A quantificação foi feita por meio de curvas analíticas no intervalo de concentração de 0 a 40 mg kg(-1) (para ambos os elementos) no material fundido final. O método desenvolvido, não sofreu interferência matriz uma vez que as amostras foram completamente decompostas e, posteriormente secas no substrato. Os resultados para os elementos foram estatisticamente comparáveis com os obtidos por espectrometria de absorção atômica com chama (FAAS). Além disso, os resultados concordaram com os obtidos nas amostras de programas de proficiência da ASTM. Amostras reais de petróleo, fornecidas pela Petrobras, também foram analisadas. As recuperações alcançadas se encontram entre 71 e 100 por cento para as diferentes amostras, o qual pode ser considerado satisfatório devido à dificuldade em se determinar esses elementos. Os limites de quantificação (10 vezes o desvio-padrão, n=10) encontrados para o Si e Al no petróleo foram de 0,7 e 1,1 mg kg(-1), respectivamente, mostrando o potencial do método proposto para a determinação de amostras com valores mais elevados destes elementos.
It is important to determine silicon and aluminum at different levels in crude oils because of trace amounts of these elements may produce adverse effects in oil refining either by causing corrosion or by contaminating and affecting the quality of the refined products. Energy dispersive X-ray fluorescence spectrometry (EDXRF) was used to enable a reliable method for determination of Si and Al in crude oil, where these elements are found mainly in the form of solid aluminosilicate particles dispersed in the sample. Since the analytes could not be determined directly in the oil without interference, the fusing the crude oil samples was made using lithium tetraborate. Then, the fused samples were placed in the center of 10 mm diameter filter paper that were sandwiched between two polypropylene film foils and attached to the instrument cell for measurements. Quantification was made by using analytical curves in the concentration range from 0 to 40 mg kg (-1) (for both elements) in the final fused material. The method developed did not suffer from matrix effect once the sample matrix was completely decomposed and the sample solution dried in the substrate before measurements. The results for the elements were statistically comparable to the ones obtained by flame atomic absorption spectrometry (FAAS). In addition, for proficiency test samples, the results were in accordance to the ones reported by ASTM proficiency programs. Real samples of oil provided by Petrobras Company also were analyzed. Recoveries were achieved between 71 and 100 percent for different samples, which can be considerable satisfactory because of the difficulty in determine those elements. The limits of quantification (10 times the standard deviation. N = 10) found for silicon and aluminum in the oil were of 0.7 and 1.1 mg kg (-1), respectively, showing the potential of the proposed method to screen for samples with higher amounts of these elements.

Trace elements are involved in a variety of biochemical processes essential to life and are required in minute amounts. There are no data available on the use of handheld X-ray fluorescence (XRF) spectrometry to determine concentrations of important trace elements in ovine livers. The aim of this study was to ascertain if the handheld X-ray fluorescence spectrometer will provide reliable concentrations of certain essential trace elements in the livers of sheep. Sheep livers (n=30) were obtained from abattoirs. Wet liver samples taken from 30 liver specimens were blended until homogeneity was achieved. An aliquot of the homogenised liver samples were oven dried at 50°C until a constant mass and were then pulverised using a mortar and pestle to obtain a fine powder. In addition, homogenised liver samples (n = 30) were also submitted for dry ashing. All the prepared liver samples (i.e. wet blended, oven dried and dry ashed) were then analysed using a handheld X-ray fluorescence spectrometer to determine concentrations of copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), selenium (Se) and zinc (Zn). A reference laboratory analysed the same liver samples using ICP-MS to determine the concentrations of the above mentioned trace elements (control). The means (mg/kg) of the ICP-MS results on a dry matter basis were: Cu (505), Fe (351), Mn (12.3), Mo (3.8), Se (1.8) and Zn (168). The means (mg/kg) of the XRF oven-dried results were: Cu (502), Fe (289), Mn (11.7), Mo (1.6) and Zn (141.9). Selenium could not be detected in oven-dried samples when using the XRF. The intra-sample coefficients of variation were similar between ICP-MS and XRF for oven dried samples for Cu, Fe and Zn and are within the same order of magnitude for all elements in dry ashed samples when comparing ICP-MS to XRF. However, the intra-sample coefficients of variation for Mn and Mo were approximately an order of magnitude larger using XRF. Although the precision for Se appears to be good when using XRF on dry ashed samples, Se was only detected in a few samples, so this value is not representative of the overall precision of XRF using the dry ashed preparation procedure for Se determination. Selenium was not detectable using XRF on wet blended and oven dried samples. The intra-sample coefficient of variation for Se was relatively high using ICP-MS, suggesting that even the current ‘gold standard’ in detecting trace-elements may be imprecise in measuring Se. Overall, this suggests that the precision of sampling using XRF is relatively good for only Cu, Fe and Zn and relatively poor for Mn and Mo. Furthermore, XRF cannot be reliably used for measuring Se. Bayesian correlation were used to determine the best correlation between XRF and ICP-MS data. Bayesian correlation results are summarised by the median sample Pearson product-moment correlation coefficient (r), the 95% lower (LHPDI) and upper (UHPDI) highest posterior density intervals, the square of the sample correlation coefficient (r2), and the probability that the correlation coefficient is positive. Overall, the oven-dried preparation procedure for XRF appeared to provide the best correlation with the ICP-MS data. For Cu and Zn these correlations were strong and the XRF method may represent a suitable substitute for ICP-MS. For Mn and Fe the correlations were moderately strong and the XRF method may be suitable depending upon the intended application. For Mo the correlation was moderate and XRF cannot be recommended. For Se no XRF method was suitable. The advantage of handheld X-ray spectrometry is that the turnaround time of samples is reduced a great deal. Instead of submitting samples to a laboratory and waiting for results, samples can be analysed more rapidly with the use of a handheld X-ray fluorescence spectrometer.
Dissertation (MSc)--University of Pretoria, 2016.
Paraclinical Sciences
MSc
Unrestricted

PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO
COORDENAÇÃO DE APERFEIÇOAMENTO DO PESSOAL DE ENSINO SUPERIOR
PROGRAMA DE SUPORTE À PÓS-GRADUAÇÃO DE INSTS. DE ENSINO
O ferro é extraído sob a forma de minério de ferro, sendo 99 por cento utilizado na indústria siderúrgica. Os documentos normativos existentes indicam a volumetria como à técnica analítica para quantificar o teor de ferro em minério de ferro, com exceção da ISO 9516-1: 2003, que, recomenda a espectrometria de fluorescência de raios-X por comprimento de onda (WDXRF). Na literatura são descritos estudos utilizando a espectrometria de fluorescência de raios-X por dispersão de energia (EDXRF) para quantificar ferro em minério de ferro, mas em nenhuma destas publicações é caracterizada a confiabilidade metrológica e a incerteza de medição, sendo outros aspectos importantes na seleção de um método analítico o impacto económico e tempo de análise. No presente trabalho realizou-se um estudo comparativo de impacto económico, tempo de análise e desempenho metrológico na quantificação de ferro em minério de ferro por meio da técnica de EDXRF, comparando-o com a espectrofotometria de absorção molecular e volumetria (titulação com dicromato de potássio), abrangendo a incerteza de medição e a avaliação de parâmetros de validação para EDXRF. A análise volumétrica foi realizado baseado nas normas ANBT NBR 8577:2011 e ASTM E246:2010. Na espectrofotometria de absorção molecular, adaptou-se o método da ortofenantrolina descrito na norma ABNT NBR 13934:1997. Nas outras técnicas precisam-se da abertura da amostra, na EDXRF, as amostras foram preparadas na forma de pastilha (pó de minério prensado). Os métodos avaliados apresentaram desempenhos metrológicos equivalentes, os melhores indicadores de custo e tempo em longo prazo foram observados para o método por EDXRF na quantificação do teor de ferro em minério.
After its extraction in the form of iron ore, 99 per cent of the iron is employed in the steel industry. The normative documents existents recommend to volumetry as the technical analytic for quantification of iron in iron ore, with the exception of ISO 9516-1: 2003, which recommends the fluorescence spectrometry X-ray wavelength (WDXRF). In literature, there are studies using energy dispersive Xray fluorescence spectrometry (EDXRF) to quantify iron in iron ore, but none of these is characterized by complete validation and measurement uncertainty. Other aspects to be considered when selecting an analytical method are the financial cost and the time for analysis. In this work it is carried out a comparative study of financial cost, time analysis and metrological performance on quantification of iron ore through the EDXRF technique, in comparison with the results obtained by molecular absorption spectrophotometry and volumetry (titration with potassium dichromate), including measurement uncertainty evaluation and some parameter of validation for EDXRF. The molecular absorption spectrophotometry measurements were performed by colorimetric orthophenanthroline method. Unlike the other approaches that require sample preparation with acid, for EDXRF measurements, samples were prepared in tablet form (pressed iron ore powder). The evaluated methods presented equivalent metrological performances on determining iron in ore, but the best long-term outcome for cost was observed in the results obtained by EDXRF method.

Ce travail s'est inscrit dans le cadre d’un projet de recherche qui vise à synthétiser et caractériser de nouveaux matériaux hybrides organiques-inorganiques pouvant être utilisés dans la fabrication de cellules photovoltaïques, mais avec des éléments moins polluants que les composés actuellement proposés. Pour cela nous avons élaboré et étudié deux nouveaux composés à base d'étain : le bis tétraméthylammonium hexabromostannate ([N(CH₃)₄]₂SnBr₆), et le bis-tétraéthylammonium hexabromostannate ([CH₃-CH₂]₄SnBr₆). Les études expérimentales sont basées sur des analyses thermiques (ATD, DSC, ATG), la spectrométrie par dispersion en énergie (EDX), la diffraction de rayons X sur poudre et sur monocristal, les spectrométries vibrationnelles (infrarouge et Raman), la spectrométrie d’impédance complexe et la spectrométrie UV-Visible.Il est apparu que [N(CH₃)₄]₂SnBr₆ est de symétrie cubique du type K₂PtCl₆. Il est constitué d'octaèdres SnBr₆²- non connectés entre eux, séparés par des tétraméthylammoniums, pouvant être considéré comme dérivé d'une structure pérovskite dans laquelle la moitié des sites de symétrie octaédriques sont occupés par des SnBr₆²- et la moitié par des lacunes (structure pérovskite 0D). Cet arrangement laisse ainsi de très larges volumes libres de tout atome, et nous avons même montré qu'il présente des canaux ouverts infinis de large section (0,5 nm de diamètre), pouvant ainsi être considéré comme poreux. Les analyses vibrationnelles couplées à des calculs ab-initio sur l'octaèdre SnBr₆²- et l'ion tétraméthylammonium (TMA+) ont permis d'expliquer sans ambiguïté les spectres et de conclure à l'existence de désordre local. Les signaux infrarouges, Raman et EDX suggèrent aussi la présence d’OH- ou d’'eau, probablement en relation avec la structure lacunaire. Il a été montré que le composé subit une transition de phase réversible à plus haute température (vers 100°C). Les études vibrationnelles confirment la transition de phase, de même que les études des propriétés diélectriques. Le gap (2,31 eV) est proche de la largeur de la bande interdite 2,7 eV du semi-conducteur Cs₂SnBr₆ utilisé dans les cellules solaires.Le bis-tétraéthylammonium hexabromostannate [CH₃-CH₂]₄SnBr₆ à température ambiante présente une structure (rhomboédrique) composée également d'octaèdres SnBr₆²- non connectés, mais d'arrangement structural compact, contrairement au composé au TMA. Son étude en température révèle deux transitions réversibles mais avec fortes hystérésis à 262K/239K et à 362K/307K (chauffage/refroidissement). Son énergie de gap est égale à 2,51 eV
This work is part of a research project that aims to synthesize and characterize new organic-inorganic hybrid materials that can be used in the manufacture of photovoltaic cells, but with less polluting elements than the compounds currently proposed. For this we have developed and studied two new compounds based on tin : bis tetramethylammonium hexabromostannate ([N(CH₃)₄]₂SnBr₆), and bis-tetraethylammonium hexabromostannate ([CH₃-CH₂]₄SnBr₆). The experimental studies are based on thermal measurements (ATD, DSC, ATG), energy dispersion spectrometry (EDX), powder and single crystal X-ray diffraction, vibrational spectrometries (infrared and Raman), complex impedance spectrometry, and UV-Visible spectrometry.It appeared that [N(CH₃)₄]₂SnBr₆ is of cubic symmetry of the K₂PtCl₆ type. It consists of unconnected SnBr₆²- octahedra, separated by tetramethylammoniums, which can be considered to be derived from a perovskite structure in which half of the sites of octahedral symmetry are occupied by SnBr₆²- and half by vacancies (perovskite structure 0D). This arrangement thus leaves very large volumes free of any atom, and we have even shown that it has infinite open channels of large section (0,5 nm in diameter) ; it can thus be considered as a porous material. The vibrational analyzes coupled with ab-initio calculations on the SnBr₆²- octahedron and the tetramethylammonium ion (TMA+) made it possible to unambiguously explain the spectra and to conclude to the existence of local disorder. Infrared, Raman and EDX signals also suggest the presence of OH- or water, probably related to the porous structure. It has been shown that the compound undergoes a reversible phase transition at a higher temperature (around 100°C). Vibrational studies confirm the phase transition, as do studies of dielectric properties. The gap (2,31 eV) is close to the width of the 2,7 eV forbidden band of the Cs₂SnBr₆ semiconductor used in solar cells.Bis-tetraethylammonium hexabromostannate [CH₃-CH₂]₄SnBr₆ at room temperature exhibits a (rhombohedral) structure also composed of non-connected SnBr₆²- octahedra, but of compact structural arrangement, unlike the compound with TMA. Its temperature study reveals two reversible transitions but with strong hysteresis at 262K / 239K and at 362K / 307K (heating / cooling). Its gap energy is equal to 2,51 eV

O desenvolvimento e validação de métodos analíticos é um procedimento necessário quando um método não normalizado é utilizado por um laboratório de ensaios. A validação de métodos também é um requisito específico da norma ABNT NBR ISO/IEC 17025, que determina os requisitos gerais para a competência dos laboratórios de ensaio e calibração. O objetivo da validação é demonstrar que o método analítico, nas condições em que é executado, produz resultados com a exatidão requerida. O Laboratório de Corrosão, Proteção e Reciclagem de Materiais (LACOR), da UFRGS, tem o ensaio de determinação de metais por fluorescência de raios X, acreditado pelo CGCRE/INMETRO, conforme ABNT NBR ISO/IEC 17025. O ensaio é feito usando o método de espectrometria de fluorescência de raios X por dispersão de energia (EDXRF). Este método, contudo, não é normalizado e, portanto, o mesmo foi validado, neste trabalho de pesquisa, para atender a este requisito. A validação foi feita com base no documento orientativo DOQ-CGCRE-08 e no guia EURACHEM. Os parâmetros de validação, para o ensaio quantitativo por EDXRF, que foram calculados neste trabalho são: seletividade; limite de detecção (LD) e limite de quantificação (LQ); linearidade e faixa de trabalho; veracidade de medição (tendência, erro normalizado, Z-score e comparação com método de referência) e precisão (repetibilidade, precisão intermediária e reprodutibilidade). Além disso, foi desenvolvida uma metodologia de cálculo de incerteza de medição para o ensaio por EDXRF Os resultados obtidos neste estudo demonstram que o método EDXRF, usado na determinação de metais em aços, é um método não normalizado validado e compatível com os resultados obtidos com os métodos de referência: espectrometria de fluorescência de raios X por dispersão de comprimento de onda (WDXRF), fotométricos e espectrometria de absorção atômica (AAS). Inclusive, o WDXRF é um método de referência usado em muitas normas internacionais, que descrevem métodos de análise de aços por fluorescência de raios X, como ASTM E572 ou ASTM E1085. O estudo desenvolvido nesta dissertação permitiu que o LACOR mantivesse sua acreditação no ensaio de determinação de metais por fluorescência de raios X, na avaliação do CGCRE/INMETRO, no presente ano. Outros frutos deste trabalho foram a confecção das curvas de calibração do espectrômetro NITON XL3t GOLDD+ e a revisão do procedimento de ensaio, onde esses novos conhecimentos sobre a técnica EDXRF foram aplicados. Futuramente, este trabalho pode ser usado por outros pesquisadores para desenvolver estudos em outras matrizes metálicas, como cobre, alumínio, titânio ou níquel, e, também, em outras áreas de aplicação como jóias, reciclagem de materiais metálicos ou, até mesmo, para análise elementar de resíduos retidos em membranas de troca iônica.
The development and validation of analytical methods is a required procedure when a non-standard method is used by a testing laboratory. Method validation is also a specific requirement of the ABNT NBR ISO / IEC 17025, which determines the general requirements for the competence of testing and calibration laboratories. The purpose of validation is to demonstrate that the analytical method, under the conditions in which it is performed, produces results with the required accuracy. The Corrosion, Protection and Recycling Materials Laboratory (LACOR), at UFRGS, has the X-ray fluorescence metal analysis, accredited by CGCRE / INMETRO, according to ABNT NBR ISO / IEC 17025. The test is performed using Energy Dispersive X-Ray Fluorescence spectrometry, EDXRF method. This method, however, is not standardized; therefore, it was validated in this research to meet this requirement. The validation was based on the DOQ-CGCRE-08 document and the EURACHEM guide. The method performance calculated in this study for quantitative testing by EDXRF are: selectivity; limit of detection (LOD) and limit of quantification (LOQ); linearity and working range; trueness (bias, normalized error, Z-score and comparison with reference method) and precision (repeatability, intermediate precision and reproducibility). In addition, a measurement uncertainty calculation methodology was developed for the EDXRF testing The results obtained in this study demonstrate that the EDXRF method, used in the determination in the chemical analysis of steels, is a validated non-standard method and compatible with the results obtained with the reference methods: Wavelength Dispersive X-Ray Fluorescence spectrometry (WDXRF), photometric and atomic absorption spectrometry (AAS). In addition, WDXRF is a reference method used in many international standards, which describes analysis of steels by X-ray fluorescence spectrometry such ASTM E572 or ASTM E1085. The study developed in this dissertation allowed LACOR to maintain its accreditation in the test of metal by X-ray fluorescence analysis, in the CGCRE / INMETRO audit, this year. Other fruits of this work were the preparation of calibration curves of NITON XL3t GOLDD + spectrometer and complete revision of testing procedure, where this new knowledge about the EDXRF technique was applied. In the future, this work can be used by other researchers to develop studies in other base metals such as copper, aluminum, titanium or nickel, and also in other areas of application such as jewelry, recycling of metallic materials or even for analysis elemental residues retained in ion exchange membranes.

Disertační práce se zabývá studiem strukturních a mechanických vlastností anorganických materiálů. Cílem je nalezení jednotlivých fází ve zkoumaném materiálu a hlavně lokalizace (mechanicky) nejslabšího místa, jeho ovlivnění a následně výroba materiálu o lepších mechanických vlastnostech. Z důvodu velkého množství použitých metod je základní teorie vložena vždy na začátku příslušné kapitoly. Taktéž z důvodu značného množství výsledků jsou na konci kapitol uvedeny dílčí závěry. Práce je rozdělena na tři části, kdy první se zabývá seznámením s možnostmi modelování mikro-mechanických vlastností a provedením experimentů umožňujících posouzení rozsahu platnosti některého modelu. V druhé části je provedeno shrnutí současných možností indentačních zkoušek pro měření mechanických vlastností strukturních složek betonu a praktické zvládnutí metodiky vhodné k užití pro výzkum materiálů zkoumaných domovským pracovištěm. V třetí části je navržena metoda identifikace nejslabších článků struktury anorganických pojiv a její ověření na konkrétním materiálu zkoumaném na domovském pracovišti. V této dizertační práci jsou použity tyto metody: kalorimetrie, ultrazvukové testování, jednoosá pevnost v tlaku, nanoindentace, korelativní mikroskopie a rastrovací elektronová mikroskopie s energiově disperzním spektrometrem. Dílčími výsledky jsou kompletní charakterizace cementových materiálů, upřesnění stávajících poznatků a nalezení optimálního postupu pro charakterizaci. Hlavním výsledkem je inovativní přístup vedoucí k pozitivnímu ovlivnění materiálu.

The dissertation thesis deals with the modification of the surface of advanced magnesium alloys with Ni-P based coatings. At the beginning of the theoretical part, the structures of the used magnesium alloys and the influence of individual alloying elements on their properties are characterized. In the following part of the thesis the current knowledge in the field of electroless deposition on metal substrates is summarized. The theoretical part of the thesis is closed with contemporary research study in the field of clarification and determination of possible mechanism of electroless deposition. For the subsequent investigation of the mechanism of electroless deposition on magnesium alloys, it was necessary to characterize the microstructure and composition of individual magnesium alloys in the first phase of the experimental part. The exact composition of elements was determined using glow discharge optical emission spectroscopy and scanning electron microscopy with EDS was used for composition of phases of magnesium alloys. Using scanning electron microscopy and detailed elemental analysis of the coated magnesium substrate, it was found that for optimal Ni-P coating deposition on magnesium alloys, acid pickling prior coating is required in a mixture of acetic acid and sodium nitrate. Using the XPS method, it was found that the phosphorus atom in the sodium dihydride-diphosphate reducing agent has a + V charge. 4 At the end of the experimental part scanning electron microscopy and detailed elemental analyses were used for monitoring of the Ni-P particles nucleation and growth in the first 120 seconds of the coating process.

The best spatial resolution, for a microanalysis with a scanning electron microscope (SEM), is achieved by using a low voltage electron beam. But the x-ray microanalysis was developed for high electron beam energy (greater than 10 keV). Also, the specimen will often contain light and medium elements and the analyst will have to use a mixture of K, L, and sometime M x-ray peaks for the x-ray microanalysis. With a mixture of family lines, it will be common to have secondary fluorescence x-rays emission by K-L and L-K interactions. The accuracy of the fluorescence correction models presently used by the analyst are not well known for these interactions. This work shows that the modified secondary fluorescence x-rays emission correction models can improve the accuracy of the microanalysis for K-L and L-K interactions. The general equation derived in this work allows the identification of three factors which influence the secondary fluorescence x-rays emission. The fluorescence production factor can be used to predict the importance of the secondary fluorescence x-rays emission. A large value of the fluorescence production factor indicates that a fluorescence correction is needed. Another disadvantage of using a low voltage is that there are more frequent occurrences of x-ray peaks overlap. A new microanalysis instruments that combines the high-spatial resolution and high-energy resolution for x-ray detection is needed. The microcalorimeter energy-dispersive spectrometer (uEDS) should improve the low voltage microanalysis, but the maturity of this technology has to be evaluated first. One of the first commercial uEDS for x-ray microanalysis in a SEM is studied and analyzed in this work. This commercial uEDS has an excellent energy resolution (15 eV) and can detect x-rays of low energy. This x-ray detector can be used as a high-spatial resolution and high-energy resolution microanalysis instrument. There are still hurdles that this technology must overcome before i
Pour la microanalyse par rayons X avec un microscope électronique à balayage (MEB), la meilleure résolution spatiale est obtenue à bas voltage. Cependant, la microanalyse par rayons X a été développée pour des grandes énergies du faisceau d'électrons (plus grandes que 10 keV). De plus, les échantillons analysés contiennent souvent des éléments légers et moyens. L'analyste va devoir utiliser un mélange de pics de rayons X K, L et parfois M pour la microanalyse par rayons X. Avec un aussi grand nombre de pics, l'émission de fluorescence secondaire de rayons X par des interactions K-L et L-K est inévitable. La précision des modèles de correction de la fluorescence utilisés présentement n'est pas bien quantifiée pour ces types d'interactions. Les modifications apportées, dans le cadre de ce travail, aux modèles de correction de la fluorescence améliorent la précision des résultats de la microanalyse pour les interactions K-L et L-K. L'équation générale dérivée dans ce travail permet l'identification de trois facteurs qui influencent l'émission de fluorescence secondaire de rayons X. Le facteur de production de fluorescence est utilisé pour prédire l'importance de l'émission de fluorescence de rayons X. Une grande valeur de ce facteur indique que la correction de fluorescence est nécessaire. Un autre désavantage d'utiliser une basse tension est le chevauchement des pics de rayons X qui se produit plus fréquemment. Un nouvel instrument de microanalyse qui combine une grande résolution spatiale et une grande résolution en énergie pour la détection des rayons X est nécessaire. Un spectromètre microcalorimétrique à dispersion d'énergie des rayons X (uEDS) devrait améliorer la microanalyse à basse tension, mais la maturité de cette technologie doit être évaluée. L'un des premiers spectromètre uEDS commercial pour la microanalyse par rayons X dans un MEB est étudié et analysé dans ce travail. Cet uEDS commercial$

Ce travail a pour but de demontrer que le confort apporte en spectrometrie de rayons x dispersive en energie (technique eds) par le developpement d'appareillages de plus en plus instrumentes n'est qu'apparent. Nous avons demontre en particulier que si l'obtention de resultats reproductibles est possible en quelques centaines de secondes, et ce meme en l'absence de temoins de reference, c'est en grande partie parce que les methodes informatiques associees a ce type de technique de microcaracterisation procedent a un lissage systematique des spectres. Il a ete possible de preciser de plus que la recherche systematique de spectrometres de plus en plus performants ne semble pas apporter des resultats de meilleure qualite pour la detection et le dosage d'elements de faible numero atomique. Notre demarche est argumentee autour de: la selection, a partir d'une demarche strictement analytique, de temoins de reference de materiaux metalliques et de materiaux mineraux; une maitrise des parametres experimentaux en amont du detecteur, qui a pu deboucher sur un protocole experimental parfaitement defini; une meilleure connaissance du role par l'etat de surface des materiaux etudies en portant une attention particuliere au role des effets de charge superficiels; une meilleure connaissance des problemes de deconvolution et d'analyse comparative des resultats, realisee en aval du detecteur. La comparaison avec les donnees de base fournies par la spectrometrie de rayonx x dispersive en longueur d'onde (technique wds) a guide la description de cette approche. L'ensemble des resultats obtenus a permis de caracteriser, par comparaison systematique avec des donnees de reference, les phases presentes dans des alliages refractaires type fe ni cr x apres differents traitements thermiques sous atmosphere carburante controlee ou non controlee (air ambiant). L'accent a pu etre ainsi mis sur le probleme important de la detection et du dosage des elements de faible numero atomique, tel que le carbone (apporte en particulier par l'atmosphere carburante) ou l'oxygene (apporte par l'atmosphere oxydante). L'ensemble de ces travaux fondes sur la maitrise de la technologie eds doit pouvoir avoir des repercussions analytiques en techniques wds

Doped semiconductor quantum dots (QDs) comprise an important subclass of nanomaterials in which a small quantity of impurity is added intentionally, adding another degree of freedom to alter their size-dependent physical and electronic properties. Intense, tunable, long lived and stable photoluminescence make them quintessential candidates for many opto-electronic applications including solid-state lighting, display devices and biomedical imaging. ZnSe QDs, which are blue-emitting fluorophores, were doped with Cu⁺¹ to redshift their photoluminescence (PL) to green region of the visible spectrum. These Cu-doped ZnSe QDs were then codoped with Al³⁺, Ga ³⁺ and In³⁺ to improve the PL quantum yield (QY) by eliminating the defect states originating from charge imbalance created by aliovalent doping. Codoping also resulted in further redshifting of the PL, covering most of the visible spectrum, making them potential candidates for use in solid-state lighting and as optical down converters in next generation light emitting diodes (LEDs). To better understand the optical properties of these materials, local structure around the luminescent centers was investigated by extended X-ray absorption fine structure (EXAFS). Cu was found to occupy a distorted tetrahedral site with the codopant residing in a substitutional Zn site. Based on the structural information obtained by EXAFS, density functional theory calculations (DFT) were performed to get a clear picture of the energy levels associated with the electronic transitions. Furthermore, the dynamics studies of the exciton and charge carriers were carried out to get deeper insight of the various photophysical processes involved. The fluorescence lifetime was increased approximately 10 times after doping.

The multielectron catalytic reactions often involve multimetallic clusters, where the reaction is controlled by the electronic and spin coupling between metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. A method was developed to detect X-ray emission signal from multiple elements simultaneously to probe the electronic structure and sequential chemistry that occurs between the elements. A wavelength dispersive spectrometer based on the von-Hamos geometry was used, that disperses Kβ emission signals of multiple elements onto an area detector, and enables an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the Rowland circle spectrometers, and the data is free from temporal and normalization errors, and therefore ideal to follow sequential chemistry at multiple sites. This method was applied to MnO_x based electrocatalysts, and the effect of Ni addition was investigated. Electro-deposited Mn oxide catalyses oxygen-evolution reaction (OER) and oxygen-reduction reaction (ORR) at different electrochemical potentials under alkaline condition. Incorporation of Ni reduced the low valent Mn component resulting in higher average oxidation state of Mn in MnNiOx under ORR and OER conditions, when compared to MnO _x under similar conditions. The reversibility of the electrocatalyst was also found to improve by the inclusion of Ni.

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CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Este trabalho consiste no desenvolvimento, implantação e caracterização de um Analisador Cilíndrico Dispersivo 1270 em um Espectrômetro de Perda de Energia de Elétrons (EPEE) operando na região de energia de impacto de 10 a 200 eV, que está sendo desenvolvido no Laboratório de Espectroscopia Atômica e Molecular – LEAM da UFJF. Além do analisador, foram também desenvolvidos diversos trabalhos para otimização do circuito de controle do canhão de elétrons monocromatizado do EPEE, o que gerou ótima estabilidade, acarretando em um ganho considerável em intensidade do feixe produzido e melhoria no manuseio do mesmo. É descrito a implementação da variação angular da plataforma giratória que apóia o Analisador Cilíndrico Dispersivo 1270, bem como a medida desta variação, e também, do sistema de injeção do feixe gasoso através de uma cânula de molibidênio isolada eletricamente, com movimento verticalem relação ao disco onde estão instalados o canhão e analisador. Os testes de desempenho do Espectrômetro foram feitos a partir da análise da resolução de Energia ΔE do EPEE. Obtivemos ótimos resultados quanto a transmissão do feixe de elétrons monocromatizado através da região de colisão chegando até a região de detecção do espectrômetro. É descrito, também, uma avaliação das melhorias feitas no Circuito de Controle do Canhão de Elétrons Monocromatizado, obtendo excelentes resultados quanto a intensidade do feixe de elétrons na faixa de energia de 0,1-100 eV.
This work describes the development, implementation and characterization of a Cylindrical Dispersive Analyzer 1270 on a Electron Energy Loss Spectrometer (EELS) operating in the region of impact energy from 10 to 200eV, which is being developed at the Laboratory of Atomic Spectroscopy and Molecular – LEAM UFJF. In the analyzer, several studies have also been developed to optimize the control circuit of the monochromatized electron gun of the EELS, which generated great stability, resulting in a considerable gain in intensity of the beam produced and improved handling. We describe the implementation of the angular variation of the turntable that supports the Cylindrical Dispersive Analyzer 1270, and the measure of variation, and also injection system of the gas through a beam cannula molybdenum electrically isolated, with vertical movement relative to disk where the monochromatized electron gun and the energy analyzer of electrons are installed. Performance tests of the spectrometer were made from the analysis of the energy resolution ΔE of the EELS. We obtained excellent results about transmission of the electron beam across the monochromatization region collision reaching the detection region of the spectrometer. We describe also an assessment of the improvements made in the Control Circuit of the Monochromatized Electron Gun, obtaining excellent results for the intensity of the electron beam in the energy range 0.1-100 eV.

O objetivo deste estudo in vitro foi avaliar e comparar a microestrutura e a composição mineral do esmalte e da dentina de dentes decíduos e permanentes. Terceiros molares hígidos e segundos molares decíduos foram selecionados e distribuídos aleatoriamente em grupos, de acordo com o método de análise dos substratos utilizado: Microscopia Eletrônica de Varredura (MEV), Espectroscopia de Energia Dispersiva de Raio X (EDX), Difração de Raio X (DRX) e Microscopia Óptica (MO). Foi realizada comparação qualitativa e quantitativa da estrutura dental. As medidas de densidade numérica e diâmetro dos prismas de esmalte/túbulos dentinários e, de espessura do esmalte, dentina e dentina peritubular foram realizadas por meio de fotomicrografias obtidas pela MEV. Os resultados obtidos por meio da SEM foram analisados estatisticamente pelo teste não-paramétrico de Kruskal-Wallis. A quantidade relativa de íons cálcio (Ca) e fósforo (P) foram determinadas por meio de EDX e as fases químicas presentes em ambos os substratos, por análise de DRX. O valor das medidas de espessura observado para o esmalte e dentina dos dentes decíduos foi de 1.14 mm e 3.02 mm, respectivamente. Para os dentes permanentes, obtiveram-se valores de 2.58 mm para o esmalte e 5.95 mm para a dentina. Com relação ao diâmetro da cabeça dos prismas de esmalte, os resultados foram estatisticamente semelhantes para os dentes decíduos e permanentes, demonstrando uma ligeira diminuição do diâmetro da superfície externa para a região próxima a junção amelodentinária (JAD). A densidade numérica dos prismas foi maior nos dentes decíduos, principalmente próximo à JAD, sendo estatisticamente diferente dos valores observados nos dentes permanentes, independente da região analisada. Na análise do diâmetro e densidade numérica dos túbulos dentinários verificou-se semelhança estatística entre os dentes decíduos e permanentes, havendo aumento gradativo do número de túbulos a partir da JAD em direção a região próxima a polpa. A espessura da dentina peritubular, na região próxima a JAD e central foi, respectivamente, 0.91 e 0.59 mm nos dentes decíduos 1.16 e 0.98 mm nos dentes permanentes. A porcentagem de Ca e P foi maior nos dentes permanentes. Observou-se ainda, que a quantidade de colágeno nos dentes decíduos foi aparentemente menor quando analisados por meio da MO. De acordo com os resultados obtidos neste estudo, pode-se concluir que, de maneira geral, os dentes decíduos apresentam menor porcentagem de Ca e P, menor espessura de esmalte e dentina, maior densidade numérica de prismas e dentina peritubular mais delgada quando comparada aos dentes permanentes.
This study evaluated in vitro the microstructure and mineral composition of dental enamel and dentin comparing the permanent teeth with the deciduous teeth. Sound third molars and second primary molars were selected and randomly assigned to the following groups, according to the analysis methods of the substrates performed: Scanning Electron Microscopy (SEM), X-Ray diffraction (XRD), Energy dispersive X-ray spectrometer (EDS) and Optical Microscopy (OP). A qualitative and quantitative comparison of the dental structure was done. The measurements of the number and diameter of prisms/tubules, thickness of enamel, dentin and peritubular dentin were done in SEM photomicrographs. The microscopic findings were analyzed statistically by a non-parametric test (Kruskal- Wallis). The relative amounts of calcium (Ca) and phosphorus (P) were determined by EDS investigation. Phase present in both types of teeth were observed by the XRD analysis. The mean thickness measurements observed in the deciduous teeth enamel and dentin was, respectively, 1.14 mm and 3.02 mm and in the permanent teeth, 2.58 mm and 5.95 mm. The mean rod head diameter in deciduous teeth was statistically similar to that of permanent teeth enamel, and a slightly decrease from the outer enamel surface to the region next to the enameldentine junction was assessed. The numerical density of enamel rods was higher in the deciduous teeth, mainly near EDJ, that showed statistically significant difference. The mean tubules number and diameter in deciduous teeth were statistically similar to that of permanent teeth, and this numerical density increased from the EDJ to the region near the pulp. The mean thickness measurements of peritubular dentin observed in the regions near EDJ and central were, respectively, 0.91 and 0.59 mm for the primary teeth / 1.16 and 0.98 mm for the permanent teeth. The percentage of Ca and P was higher in the permanent teeth. The collagen level was apparently lower in deciduous teeth when analyzed by OP. The primary teeth structure showed a lower level of Ca and P and a thinner enamel and dentin thickness. The deciduous enamel presented higher numerical density of rods. The peritubular dentin was thicker in the permanent teeth.

Nous avons developpe les procedures experimentales et de traitement de donnees requises dans le cadre d'etudes danes (diffraction anomalous near edge spectroscopy) appliquees a l'etude d'echantillons tres absorbants sous forme de poudres et de monocristaux. Nous avons pour cela considere deux procedures experimentales differentes, en optiques (i) monochromatique et (ii) dispersive en energie, le but ultime etant d'obtenir des donnees de bonne qualite, reproductibles, en un temps de mesure le plus court possible. Nous avons pu montrer que la diffraction dispersive en energie permet d'effectuer des mesures rapides dans des conditions experimentales identiques pour toutes les energies mais la qualite des donnees obtenues est moindre. Aussi afin d'effectuer un traitement quantitatif des donnees, les intensites diffractees doivent etre preferablement mesurees en faisceau monochromatique. Bien que les temps de collecte soient plus longs, les informations obtenues y sont de meilleure qualite, en particulier au niveau de la reproductibilite, du rapport signal / bruit et de la resolution en energie. Les developpements instrumentaux que nous avons effectues ont ete illustres dans le cas limite des echantillons absorbants, sous forme de poudres et de monocristaux. Des oxydes de metaux de transitions, dans lesquels les metaux presentent differents etats de valence en des sites cristallographiques distincts, ont ete choisis. Des spectres de bonne qualite ont ete obtenus lors des diverses mesures sur ces composes et des analyses quantitatives ont pu etre menees dans les differents cas. L'importance d'une correction extremement precise de l'absorption avant tout traitement de donnees est soulignee, le signal anomal etant noye dans celui de l'absorption. Une discussion des possibilites et des limites des analyses danes est egalement effectuee.

Thermo-stabilized lignin fibers from pH-fractionated softwood kraft lignin were carbonized to various temperatures during thermomechanical analysis (TMA) under static and increasing load and different rates of heating. The aim was to optimize the carbonization process to obtain suitable carbon fiber material with good mechanical strength potential (high tensile strength and high E-modulus). The carbon fibers were therefore mainly evaluated of mechanical strength in Dia-Stron uniaxial tensile testing. In addition, chemical composition, in terms of functional groups, and elemental (atomic) composition was studied in Fourier transform infrared spectroscopy (FTIR) and in energy-dispersive X-ray spectroscopy (EDS), respectively. The structure of carbon fibers was imaged in scanning electron microscope (SEM) and light microscopy. Thermogravimetrical analysis was performed on thermo-stabilized lignin fibers to evaluate the loss of mass and to calculate the stress-changes and diameter-changes that occur during carbonization. The TMA-analysis of the deformation showed, for thermo-stabilized lignin fibers, a characteristic behavior of contraction during carbonization. Carbonization temperatures above 1000°C seemed most efficient in terms of E-modulus and tensile strength whereas rate of heating did not matter considerably. The E-modulus for the fibers was improved significantly by slowly increasing the load during the carbonization. The tensile strength remained however unchanged. The FTIR-analysis indicated that many functional groups, mainly oxygen containing, dissociate from the lignin polymers during carbonization. The EDS supported this by showing that the oxygen content decreased. Accordingly, the relative carbon content increased passively to around 90% at 1000°C. Aromatic structures in the carbon fibers are thought to contribute to the mechanical strength and are likely formed during the carbonization. However, the FTIR result showed no evident signs that aromatic structures had been formed, possible due to some difficulties with the KBr-method. In the SEM and light microscopy imaging one could observe that porous formations on the surface of the fibers increased as the temperature increased in the carbonization. These formations may have affected the mechanical strength of the carbon fibers, mainly tensile strength. The carbonization process was optimized in the sense that any heating rate can be used. No restriction in production speed exists. The carbonization should be run to at least 1000°C to achieve maximum mechanical strength, both in E-modulus and tensile strength. To improve the E-modulus further, a slowly increasing load can be applied to the lignin fibers during carbonization. The earlier the force is applied, to counteract the lignin fiber contraction that occurs (namely around 300°C), the better. However, in terms of mechanical performance, the lignin carbon fibers are still far from practical use in the industry.

by Chan Wing-yee.
Thesis (M.Phil.)--Chinese University of Hong Kong, 1993.
Includes bibliographical references (leaves 93-95).
ACKNOWLEDGEMENT --- p.i
ABSTRACT --- p.ii
Chapter CHAPTER 1 --- INTRODUCTION --- p.1
Chapter 1.1 --- General Introduction --- p.1
Chapter 1.2 --- "Clinical Significance of Fe, Cu and Zn" --- p.2
Chapter 1.3 --- Alternative Methods of Analysis --- p.5
Chapter 1.4 --- Principles of Energy Dispersive X-ray Fluorescence Spectrometry --- p.11
Chapter 1.5 --- Research Plan --- p.20
Chapter CHAPTER 2 --- EXPERIMENTAL --- p.22
Chapter 2.1 --- Energy Dispersive X-ray Fluorescence Analysis --- p.22
Chapter 2.1.1 --- Apparatus --- p.22
Chapter 2.1.2 --- Reagents --- p.25
Chapter 2.1.3 --- Procedure --- p.28
Chapter 2.2 --- Atomic Absorption Spectrometric Analysis --- p.32
Chapter 2.2.1 --- Apparatus --- p.32
Chapter 2.2.2 --- Reagents --- p.32
Chapter 2.2.3 --- Procedure --- p.34
Chapter CHAPTER 3 --- RESULTS AND DISCUSSION --- p.38
Chapter 3.1 --- Optimisation of Excitation Conditions --- p.38
Chapter 3.1.1 --- Effect of Filter --- p.38
Chapter 3.1.2 --- Effect of Tube Voltage --- p.43
Chapter 3.1.3 --- Effect of Tube Current --- p.44
Chapter 3.2 --- Optimisation of Preconcentration Procedure --- p.46
Chapter 3.2.1 --- Effect of Sample Area and Collimator Size --- p.46
Chapter 3.2.2 --- Effect of pH --- p.51
Chapter 3.2.3 --- Effect of Ligand Concentration --- p.54
Chapter 3.2.4 --- Effect of Mixing Time --- p.57
Chapter 3.2.5 --- Effect of Standing Time --- p.59
Chapter 3.2.6 --- Study of Sample Homogeneity --- p.61
Chapter 3.3 --- Optimisation for Deproteination --- p.63
Chapter 3.3.1 --- Effect of Different Protein Precipitants --- p.63
Chapter 3.3.2 --- Effect of Trichloroacetic Acid Concentration --- p.65
Chapter 3.3.3 --- Effect of Hydrochloric Acid Concentration --- p.67
Chapter 3.3.4 --- Effect of Temperature --- p.69
Chapter 3.3.5 --- Effect of Incubation Time --- p.71
Chapter 3.4 --- Study of Blanks --- p.74
Chapter 3.5 --- Construction of Calibration Curves --- p.77
Chapter 3.6 --- Determination of Detection Limit and Sensitivity --- p.84
Chapter 3.7 --- Accuracy and Reproducibility Tests --- p.86
Chapter 3.8 --- Parallel Check --- p.89
Chapter CHAPTER 4 --- CONCLUSION --- p.92
REFERENCES --- p.93

by Wong Chi Kin.
Thesis (M.Phil.)--Chinese University of Hong Kong, 1994.
Includes bibliographical references (leaves 131-133).
Acknowledgement
Abstract --- p.1
General introduction --- p.4
Part I Determination of Some Minor Elements in Cement by Energy Dispersive X-Ray Fluorescence Spectrometry
Introduction --- p.7
Experimental --- p.14
Results and discussions --- p.18
Part II Determination of Mercury in Water by Static Cold Vapour Atomic Absorption Spectrometry
Introduction --- p.78
Experimental --- p.84
Results and discussions --- p.89
Conclusion --- p.130
References --- p.131

Indiana University-Purdue University Indianapolis (IUPUI)
Provisional restorative treatment is an essential part of fixed prosthodontics. Incorporation of adequately constructed provisional restorations will enhance the success rate of definitive restorations. Repairing or replacing failed provisional restorations is a concern for both clinicians and patients. The objective of this investigation was to study the effects of alumina nanofibers reinforcement on the mechanical properties of commercially available provisional fixed partial denture PMMA material. The hypothesis was that the addition of alumina nanofibers to commercially available PMMA resin will significantly increase its flexural strength, fracture toughness, and microhardness. Alumina nanofibers at 0.0 wt %, 0.5 wt %, 1.0 wt %, and 2.5 wt % were added to commercially available provisional fixed partial material (Jet Tooth Shade). A quaternary ammonium acetate dispersant (CC-59, Goldschmidt, Janesville, WI) was added to the acrylic monomer at 0.0 wt %, 1.0 wt %, 2.0 wt % and 5.0 wt % of the nanofiber weight (12 test groups, 1 control). Samples from each group were evaluated for flexural strength, flexural modulus, fracture toughness, and microhardness. The samples were tested after storing in distilled water for 24 hours and 7 days at 37ºC. Two-way analysis of variance (ANOVA) was used to test the effects of storage time and combinations of alumina nanofiber level and quaternary ammonium acetate dispersant level on the flexural strength, fracture toughness, and microhardness of the provisional PMMA resin. Pair-wise comparisons between groups were performed using Tukey’s multiple comparisons procedure to control the overall significance level at 5 percent. Three fracture toughness samples/group were randomly selected for Energy Dispersive Spectrometry (EDS) to qualitatively evaluate the dispersion of the fibers. The data obtained from this study showed that control sample values were in the acceptance range compared with previous research. The experimental samples did not reinforce the provisional resin in the flexural strength, modulus, fracture toughness, or microhardness. There are several factors may attribute to these results, such as poor bonding at the filler/matrix interface. The more homogeneous the mixture of PMMA and fiber, the stronger the acrylic resin. In fact, the presence of poorly bonded fibers, to which little load is transferred, can be almost equivalent to voids. In addition, as seen with EDS images, alumina nanofibers had a tendency to agglomerate. The use of a magnetic stirrer was not effective in physically separating nanofibers agglomerates. Direct dispersion of alumina nanofibers in methyl methacrylate monomer and quaternary ammonium acetate dispersant was not effective in separating the nanofibers into nano-scaled single crystals. The presence of fiber agglomerates acts as a structural defect that detrimentally affects the mechanical properties. Further studies are needed to evaluate the effectiveness of fibers, dispersion techniques, and coupling agents to enhance the mechanical properties of the provisional PMMA resin.

碩士
國立清華大學
工程與系統科學系
105
This research is aim to fabricate high energy resolution N-JFET silicon drift detector used in energy dispersive x-ray spectrometer to detect characteristic X-ray of material for composition information of selected region of material. N-JFET silicon drift detector integrates FET into detector chip, which makes shorter path of signal, and decrease thermal noise for cooling with chip simultaneously. Inner leakage current can be decreased with guard ring and enhance energy resolution and quantum efficiency of low energy X-ray with shallow implanted structure; in addition, larger window area leads to thinner dead layer, which can detect lower energy to improve performance of detector. We have detected characteristic peak of 241Am(5.468 MeV), and verified α particle by calculating stopping power of α particle with different distance in air. However, we have not detected characteristic peak of 55Fe(5.898 keV) because of overhigh noise. There are two possible reason for above result; first, the signal of 55Fe(5.898 keV) is 920 times smaller than 241Am(5.468 MeV). Second, polluted surface of detector causes increase of leakage current with higher bias. Those reasons could make 55Fe(5.898 keV) covered under noise. If contamination problem can be solved with vacuum package, detecting characteristic peak of 55Fe(5.898 keV) is possible.

碩士
國立中興大學
植物病理學系所
100
Himematsutake (Agaricus blazei Murill) is a popular edible mushroom in the world. Recently, the over accumulation of heavy metals in the himematsutake had been paid attention in Taiwan. Several methods can be used to detect the accumulation of heavy metals in biological materials; however, these methods are time consuming. For detecting the heavy metals and its distribution in fruit body of himematsutake rapidly, the scanning electron microscopy-energy dispersive X-ray spectrometer (SEM-EDX) was used to analyze eight heavy metals of Cr, Ni, Cu, Zn, As, Cd, Hg and Pb in pileus and stipe of fruiting body by pieced and powdery types. Moreover, the atomic percentage of these heavy metals in pileus and stipe were be confirmed by ICP-MS. In this study, the specimens of himematsutake were collected from Taichung (USA and Japanese strain), Changhua (Japanese and Taiwanese strain), Nantou and China. The results of pieced analysis showed that the accumulation of Ni (0.040%) and As (0.009%) in pileus of fruiting body of USA strain from Taichung were significantly higher than in stipe; however, the accumulation of Hg (0.044%) and Pb (0.043%) in stipe of fruiting body of USA strain were significantly higher than pileus. The other side, the accumulation of As (0.008%) in pileus of fruiting body of Japanese strain from Taichung was significantly higher than in stipe; meanwhile, the accumulation of Ni (0.015%), Cu (0.054%), Zn (0.017%), Hg (0.034%)and Pb (0.030%) in stipe of fruiting body of Japanese strain were significantly higher than pileus. The pieced analysis of Japanese strain from Changhua indicated that Cu (0.044%), Hg (0.092%) and Pb (0.069%) in pileus were significantly higher than in stipe, and As (0.013%) and Cd (0.015%) in stipe were significantly higher than in pileus. However, the pieced analysis of Taiwanese strain from Changhua revealed that Ni (0.023%), Cu (0.041%), Zn (0.024%), As (0.013%) and Hg (0.114%) in pileus were significantly higher than in stipe. The pieced analysis of himematsutake from Natou showed that accumulation of Hg (0.088%) in pileus was significantly higher than in stipe, and the accumulation of Ni (0.029%), Cu (0.060%), Zn (0.030%) and Cd (0.025%) in stipe were significantly higher than in pileus. The pieced analysis of himematsutake from China indicated that accumulation of As (0.015%) and Hg (0.067%) in pilues were significantly higher than in stipe, and Cr (0.017%), Ni (0.023%), Cu (0.048%), Cd (0.015%) and Pb (0.052%) in stipe were significantly higher than in pileus. The results of powdery analysis showed that the accumulation of Cu (0.149%), Zn (0.059%), Hg (0.127%) and Pb (0.076%) in pileus of fruiting body of USA strain from Taichung were significantly higher than in stipe; however, the accumulation of As (0.016%), Hg (0.102%) and Pb (0.065%) in pileus of fruiting body of Japanese strain was significantly higher than in stipe. The powdery analysis of Japanese strain from Changhua indicated that Hg (0.087%) in pileus was significantly higher than in stipe, and As (0.050%) in stipe was significantly higher than in pileus. However, the powdery analysis of Taiwanese strain from Changhua revealed that Ni (0.040%), Hg (0.148%) and Pb (0.095%) in pileus were significantly higher than in stipe, and the accumulations of Cr (0.023%) and Cd (0.037%) in stipe were significantly higher than in pileus. The powdery analysis of himematsutake from Natou showed that accumulation of Pb (0.061%) in pileus wa significantly higher than in stipe. The powdery analysis of himematsutake from China indicated that accumulation of As (0.021%), Hg (0.101%) and Pb (0.076%) in pilues were significantly higher than in stipe. For ICP-MS analysis, 0.25 g of pileus and stipe of fruiting body were used for analysis. The results showed that the concentration of Cu (52.263 mg/kg), Zn (164.820 mg/kg), As (1.440 mg/kg), Cd (6.158 mg/kg) and Hg (0.178 mg/kg) in pileus of fruiting body of USA strain from Taichung were significantly higher than in stipe; however, the concentration of Cu (71.975 mg/kg), As (0.450 mg/kg) and Pb (0.260 mg/kg) in pileus of fruiting body of Japanese strain were significantly higher than in stipe. The Japanese strain from Changhua indicated that the concentration of Cu (647.847 mg/kg), Zn (121.450 mg/kg), As (2.270 mg/kg) and Hg (0.130 mg/kg) in pileus were significantly higher than in stipe; meanwhile, the is of Taiwanese strain showed that the concentration of Cu (78.553 mg/kg), Zn (214.230 mg/kg), As (1.418 mg/kg), Cd (19.530 mg/kg) and Hg (0.125 mg/kg) in pileus were significantly higher than in stipe. The analysis of himematsutake from Natou did not show significantly different between pileus and stipe of fruiting bodies. The analysis of himematsutake from China indicated that concentration of Cu (53.460 mg/kg) and Zn (124.310 mg/kg) in pilues were significantly higher than in stipe. For comparing the accumulation and distribution of heavy metals in basidiospore, pilues and stipe, the powdery analysis and ICP-MS analysis were be done. The powdery analysis showed that the heavy metals could be accumulated in basidiospores with lower atomic percentage than in pilues or stipe. Specially, Zn, Hg, and Pb were significantly different among basidiospores, pilues and stipe. Moreover, the sawdust analysis showed that the accumulations of certain heavy metals in fruiting bodies were higher than in sadust. The atomic percentage and concentration of Cu were higher in fruiting bodies than in sawdust. In this study, the analyses results from EDX were compared with the results from ICP-MS. According to correlation analysis, the atomic percentage of As, Cd and Hg based on pieced analysis have positive relationship with the ICP-MS analysis, and the coefficient of As, Cd and Hg were 0.841, 0.672 and 0.497, respectively. The other sides, the atomic percentage of Zn, As, Cd and Pb based on powdery analysis have positive relationship with the ICP-MS analysis, and the coefficient of Zn, As, Cd and Pb were 0.039, 0.277, 0.037 and 0.080. Based on the results, the EDX has potential to detect the eight heavy metals in himematsutake rapidly, and the powdery analysis might better than pieced analysis.