Made available in DSpace on 2014-10-09T12:26:15Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:48Z (GMT). No. of bitstreams: 0 / Os estudos sobre as análises de cabelos humanos têm sido assunto de contínuo interesse por se tratar de uma importante ferramenta para a avaliação de níveis de elementos traço no corpo humano. O interesse por este tecido é para o uso na monitoração de exposição ambiental ou ocupacional, para identificação da intoxicação e/ou envenenamento por metais tóxicos, na avaliação do estado nutricional, na diagnose e prevenção de doenças e nas ciências forenses. Há inúmeras vantagens na análise de cabelos quando comparados com as de outros tecidos ou fluidos biológicos, tais como sangue, urina, saliva e órgãos. Entretanto há controvérsias sobre o uso das análises de cabelos em razão da dificuldade em estabelecer os valores confiáveis de referência para as suas concentrações de elementos traço. O objetivo deste estudo foi avaliar os fatores que afetam nas concentrações de elementos em cabelos humanos e determinar os elementos em cabelos de uma população de indivíduos considerados saudáveis e residentes na área metropolitana de São Paulo, utilizando o método de análise por ativação com nêutrons (NAA). As amostras de cabelo coletadas da região occipital da cabeça foram cortadas em pequenos fragmentos, lavadas e secas para análise. As alíquotas de amostras de cabelo, juntamente com padrões sintéticos de elementos foram irradiados por 16 h sob fluxo de nêutrons térmicos de cerca de 5 x 1012 n cm-2 s-1 do reator nuclear IEA-R1 para a determinação de As, Br, Ca, Co. Cr, Cs, Cu, Fe, K, La, Na, Sb, Sc, Se e Zn. As radiações gama das amostras e dos padrões irradiados foram medidas em um espectrômetro de raios gama acoplado a um detector de Ge hiperpuro. Para avaliar a qualidade dos resultados com relação à exatidão e precisão foram analisados os materiais de referência certificados IAEA- 85 Human Hair e INCT-TL-1 Tea Leaves cujos resultados obtidos apresentaram, para a maioria dos elementos, boa concordância com os valores dos certificados (porcentagens de erros relativos inferiores a 10%) e boa precisão (coeficientes de variação inferiores a 13,6% ). As análises de uma amostra de cabelo em réplicas indicaram uma boa reprodutibilidade dos resultados, indicando a homogeneidade da amostra preparada. Os resultados das análises de cabelo com e sem tintura indicaram que a tintura afeta nos teores de elementos no cabelo em virtude da adsorção ou dessorção do elemento. As análises de cabelos de diferentes regiões da cabeça indicaram diferenças significativas para os elementos Fe, Sc, Se e Cr. Análises de cabelos de indivíduos residentes na área metropolitana de São Paulo indicaram que as concentrações de elementos nos cabelos dependem da idade, sexo e cor natural dos cabelos. Os resultados das análises de cabelos desta população mostraram que as médias das concentrações de elementos obtidas estão dentro da faixa de valores da literatura. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

The present research focuses on analyzing the possibility of implementing three dimensional woven composite (3DWC) materials in hip implants. The integration of 3DWCs in hip implants has the possibility to both extend the life-time and improve patient outcomes; by spatially varying mechanical properties to meet both biological needs as well as required mechanical loading. In this study, the bulk material properties of 3DWCs were varied based on woven composite architecture and determined using physics based models, which reflect the realistic geometries of fibers in compaction and preform. The multi-digital chain method combined with Extended Finite Elemental Analysis (XFEA) are adopted in this micro-analysis for composite design. Four different woven architectures with a combination of different existing biocompatible fiber and resins are considered in this study. The main objective is to assess the mechanical response of these biocompatible materials in the design of 3D woven architectures and determine their ability to match the required modulus at different regions of a hip implant. Results obtained show 3DWCs are viable candidates for this application. Multiple architectures and materials chosen, were able to achieve the desired mechanical response. Additional studies can use these results as a starting point and framework for further mechanical and biological testing.

The samples of garnets used in this study come from clastic sediments from the drillcores Tř-1 and T-31, selected localities of the České středohoří Mountains and garnet-bearing ultramafic rocks sampled by the drillcore T-7. The contents of the major and some minor elements were determined by an electron probe microanalyzer. The garnets from the sediments were divided into 3 groups according to the contents of the end-members: 1) pyrope-, 2) almandine - pyrope- and 3) grosular - almandine-rich. Garnets from the drillcore T-7 were classified according to individual rock types in which they occurred: lherzolite, hazburgite, pyroxenite, eclogite and granulite. Chemical analyzes of garnets displayed the presence of positive correlations Cr vs. Ca vs. Ti Mn in pyrope grains. The contents of trace elements in garnets were studied by an LA-ICP-MS. After normalization to the CI-reservoir, garnets most often show lherzolite profiles of rare earth elements. Garnets of intense red and purple colors show slightly sinusoidal REE profiles. Inclusions enclosed in garnets were studied by a scanning electron microscope. If their dimensions allowed, the major and minor elements were determined by electron microanalysis for inclusions. Inclusions of amphiboles in association with spinel group minerals, carbonates and...

The samples of garnets used in this study come from clastic sediments from the drillcores Tř-1 and T-31, selected localities of the České středohoří Mountains and garnet-bearing ultramafic rocks sampled by the drillcore T-7. The contents of the major and some minor elements were determined by an electron probe microanalyzer. The garnets from the sediments were divided into 3 groups according to the contents of the end-members: 1) pyrope-, 2) almandine - pyrope- and 3) grosular - almandine-rich. Garnets from the drillcore T-7 were classified according to individual rock types in which they occurred: lherzolite, hazburgite, pyroxenite, eclogite and granulite. Chemical analyzes of garnets displayed the presence of positive correlations Cr vs. Ca vs. Ti Mn in pyrope grains. The contents of trace elements in garnets were studied by an LA-ICP-MS. After normalization to the CI-reservoir, garnets most often show lherzolite profiles of rare earth elements. Garnets of intense red and purple colors show slightly sinusoidal REE profiles. Inclusions enclosed in garnets were studied by a scanning electron microscope. If their dimensions allowed, the major and minor elements were determined by electron microanalysis for inclusions. Inclusions of amphiboles in association with spinel group minerals, carbonates and...

This thesis aims to measure the mechanical properties of ceramics on the microscale using microcantilever beams. Focussed Ion Beam milled triangular cross-sectional beams (approximately 3 x 5 x 20µm) were fractured using a nanoindenter to measure the Young’s modulus, fracture strength, and fracture toughness. By developing the technique with a sapphire bicrystal, it was found that the mechanical properties could be successfully ascertained if correction factors were used. Experiments and theoretical work showed that sapphire and polycrystalline alumina beams undergo moisture assisted sub-critical crack growth when tested in air. Whilst corrections for the Young’s modulus have been previously reported, this is the first reported attempt to correct for the notch tip residual stress and the first to consider sub-critical crack growth. Once these factors were characterised using the sapphire bicrystal, the technique was applied to a range of different ceramics, such as polycrystalline α-alumina and silicon nitride. These are the first reported direct measurements the grain boundary toughness of these ceramics using microcantilever beams. The grain boundary toughness was correlated with the macroscopic fracture properties and the characteristics of the ceramic (grain boundary composition, impurities, and fracture mode). Two grades of α-alumina were used and the macro- and micro-scale properties extensively compared. The damage evolution during uniaxial compression of alumina was investigated in depth, and compared to a previous reported microcrack evolution model using the measured grain boundary toughness. Investigation of whether deformation twins formed during loading was undertaken and the phenomenon was shown to not occur.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a powerful technique for the analysis of organic surfaces and interfaces for many innovative technologies. However, despite recent developments, there are still many issues and challenges hindering the robust, validated use of ToF-SIMS for quantitative measurement. These include: the lack of metrology and fundamental understanding for the use of novel cluster primary ion beams such as C60ⁿ⁺ and Ar₂₀₀₀⁺; the need for validated and robust measurement protocols for difficult samples, such as those with significant micron scale surface topography; the lack of guidance on novel data analysis methods including multivariate analysis which have the potential to simplify many time-consuming and intensive analyses in industry; and the need to establish best practice to improve the accuracy of measurements. This thesis describes research undertaken to address the above challenges. Sample topography and field effects were evaluated experimentally using model conducting and insulating fibres and compared with computer simulations to provide recommendation to diagnose and reduce the effects. Two popular multivariate methods, principal component analysis (PCA) and multivariate curve resolution (MCR), were explored using mixed organic systems consisting of a simple polymer blend and complex hair fibres treated with a multi-component formulation to evaluate different multivariate and data preprocessing methods for the optimal identification, localisation and quantification of the chemical components. Finally, cluster ion beams C60ⁿ⁺ and Ar_500-2500⁺ were evaluated on an inorganic surface and an organic delta layer reference material respectively to elucidate the fundamental metrology of cluster ion sputtering and pave the way for their use in organic depth profiling. These studies provide the essential metrological foundation to address frontier issues in surface and nanoanalysis and extend the measurement capabilities of ToF-SIMS.

This thesis presents information on the subcellular localisation of two important trace elements, selenium and arsenic, in wheat, rice and rice roots for what is believed to be the first time. The general aim of this work was to illustrate the potential of using physical science techniques to solve biological problems. High resolution secondary ion mass spectrometry was undertaken using the CAMECA NanoSIMS50 with a sensitivity down to ppm concentrations and a lateral resolution of less than 100 nm. Selenium in wheat grain was found to be distributed across both the bran layer and the endosperm region with Se-rich hotspots found in the aleurone cells and a higher intensity of Se in the subaleurone region. Arsenic in rice grain was found in two key regions. In grains with high As and high dimethylarsinic acid (DMA) content, As was predominantly localised to the subaleurone region yet in lower concentration, hydroponically grown As(III)-treated grains the As was only localised to the aleurone layer near the ovular vascular trace (OVT). A combined NanoSIMS and S-XRF experiment revealed As hotspots near the OVT. A combination of high pressure freezing, high resolution secondary ion mass spectrometry and TEM was used to localise As in the roots of rice plants revealing a contrasting subcellular distribution of As and Si in the roots even though arsenite and silicic acid are transported across the plasma membranes by the same transporters. Fe plaque forms only on the root epidermis and was shown to be a strong sink for As. Colocalisation of S with As in the vacuoles of the endodermis, pericycle and xylem parenchyma supports the notion that As is stored as arsenite-phytochelatin complexes in the roots while Si is localised in the endodermis cell walls and is not strongly affected by the Lsi2 mutation.

Electron beam induced current (EBIC) and atom probe tomography (APT) were used in this study to determine electrical activities and impurity compositions at extended defects in multicrystalline silicon (mc-Si) samples. The results provide, for the first time, information regarding the chemical species present at defects whose electrical activity has previously been measured. A new APT specimen fabrication process was developed with the ability to select a specific defect for APT analysis. Development of the APT specimen fabrication process proceeded by first selecting and optimising the preferential etching for nano-scale defect delineation. Three etchants were evaluated, namely Secco, Sirtl and Dash, from which the Secco etch was selected. Three parameters were optimised to produce etch pits with geometries that meet the requirements imposed by APT specimen fabrication methods. The optimum parameters were 0.05M potassium dichromate concentration, 20°C etch temperature, and 30sec etch time. In the second stage, marking techniques were developed in order for the defects to be located throughout the APT specimen fabrication process. However, it became apparent that the conventional APT specimen fabrication method could not be used to fabricate APT specimens containing selected defects in a mc-Si sample. This led to the development of a novel APT specimen fabrication approach which allowed APT specimens to be fabricated, reproducibly, containing grain boundaries and isolated dislocations. In order to evaluate accurately iron contamination in mc-Si, four atom probe parameters were optimised to maximise detection sensitivity: the evaporation rate, the laser beam energy, the pulse repetition rate and the specimen temperature. The optimisation process can be divided in to two parts. In the first part, a matrix of pre-sharpened single-crystal silicon specimens was subjected to a variety of experimental parameters. The optimised parameters were determined to be 0.3% evaporation rate, 0.5nJ beam energy, 160kHz repetition rate and 55K specimen temperature. The second part was to determine the iron detection efficiency –the percentage of detected Fe ions that can be correctly identified as Fe– and sensitivity using these parameters to analyse a specially prepared iron calibration specimen. The values were determined to be a detection efficiency of about 35% and sensitivity of 54ppm or 2.70x10¹⁸ atom/cm³. The APT specimen fabrication process and the optimised APT analysis parameters were used to analyse four extended defects in mc-Si samples subjected to three different processing conditions, namely gold-contaminated, as-grown and phosphorus diffusion gettering (PDG). The important aspects of the analysis are listed below: • Gold was not detected at the grain boundary and its associated dislocations in the gold-contaminated specimen. The binding enthalpy of gold to such defects is thus less than 0.63eV. • Iron was not detected in any specimen. • Copper was observed at the grain boundary in the as-grown specimen in the form of individual atoms as well as clusters with diameters ranging between 4nm and 9nm. The electrical activity of the grain boundary was about 58%. • Nickel and carbon were detected at the grain boundary in the post-PDG specimen with the former having platelet structures with diameters and thicknesses ranging between 4nm-7nm and 2nm-4nm, respectively. The recombination strength of the defect was about 22%. • Two nickel clusters were found at the isolated dislocation in the post-PDG specimen. The clusters were spherical with an average diameter of 10nm. The distance between the two clusters was 35nm. The recombination strength of the defect was about 4%.

Reduced-activation ferritic steels are considered as the primary candidate materials for structural applications within nuclear fusion power plants. It is known that by mechanically alloying ferritic steel powder with Y (usually in the form of Y₂O₃) then consolidating the material by hot isostatic pressing, a nanoscale dispersion of oxygen rich nanoclusters as small as ~2nm is introduced into the microstructure. This vastly improves high temperature strength and creep resistance, and the nanoclusters also act as trapping sites for helium and point defects produced under irradiation. In this thesis, the evolution of the oxide nanoclusters in a Fe-14Cr-2W-0.3Ti & 0.3Y₂O₃ ODS alloy was investigated primarily using atom probe tomography. The microstructure was characterised at various points during processing to give an insight into the factors influencing the formation of the nanoclusters. It was found that the nanoclusters nucleated during the mechanical alloying stage, then followed near classical nucleation and growth mechanisms keeping the same composition of ~8%Y, ~12%Ti,~25%O and ~45%Cr throughout. The formation and evolution of 5-15nm grain boundary oxides was also observed, and these were shown to form first as Cr₂O₃ particles that subsequently transform into a Y-Ti-O based oxide on further processing. The influence of mechanical alloying with 0.5wt.%Fe₂Y rather than 0.3wt.%Y₂O₃ was also investigated, and this showed that there was no difference in the final microstructure produced provided the level of Ti in the starting powder was tightly controlled. Without sufficient Ti, the nanoclusters were Y-O based and ~6nm diameter. Both the Y-O and Y-Ti-O nanoclusters were moderately stable on annealing at 1200°C for up to 100 hours, with only minimal coarsening observed. Ti was found not to influence the coarsening rate of the nanoclusters significantly. The stability of the oxide nanoclusters under irradiation was investigated by using Fe²⁺ ion irradiation to simulate displacement cascade damage in the ODS-Eurofer material (the official European candidate material for testing in the ITER fusion test reactor). Doses up to ~6 dpa at 400°C were used, and there was no significant change to the nanocluster distribution. However segregation of Mn to dislocations was observed after irradiation. These results indicate that ODS steels are good candidate structural materials, as the microstructure is stable at high temperature and under irradiation. The starting powders, and processing parameters need to be tightly controlled in order to produce the optimal material for use in service.

The factors controlling the reliability of Pb-free solders when subject to thermomechanical regimes relevant to the harsh aerospace environment have been studied. Ball grid array (BGAs) typical of microelectronic devices have been manufactured in-house and subjected to isothermal ageing and thermal cycling. The BGAs comprised both Cu and Ni-Au metallizations, Pb-free Sn-Ag-Cu 400 and 600μm solder balls, FR4 and Al₂O₃ boards, and included circuits to measure resistance changes due to damage in the joints during thermal cycling. Microstructural evolution within the solders balls and complex interfacial reactions were studied in all configurations using various types of electron microscopy. The mechanical properties of the different phases formed within solder joints were studied using nanoindentation at room and elevated temperatures up to 175°C for the first time. Intermetallic compounds (IMCs) were stiff, hard and brittle with very low creep rates, while the softer primary Sn, eutectic regions and Cu metallization readily underwent creep. Two-dimensional finite element analysis (FEA) of nanoindentation was used to understand better the physical meaning of nanoindentation creep data. Reliability experiments comprised both thermal cycling and FEA of BGAs. The difference in coefficient of thermal expansion (CTE) in the BGA materials caused interfacial fatigue damage in the solder joints, which was detected primarily at the solder/metallization interface of the outermost, most strained solder joint. Accumulated creep strain per cycle at this interface was evaluated using 3D FEA of the stress-strain state of the BGA and results calibrated against experimental BGA mean lifetimes using the Coffin-Mason relationship. Nanoindentation combined with FEA has been shown to be a viable route for the rapid assessment of creep performance and lifetime in lead-free solders under aerospace thermal cycles.