Thèses sur le sujet « Layered Sample »

L’analisi scientifica è da un po’ di tempo entrata nel mondo dei beni culturali, non sono più solo gli archeologi e gli storici dell’arte a occuparsi dello studio dei reperti archeologici e storici, ma anche gli scienziati sono entrati a gamba tesa portando le loro conoscenze al servizio di questa vasta gamma di materiali. Lo studio di reperti botanici e zoologici, le competenze chimiche e mineralogiche, lo studio di fenomeni fisici, ha permesso di porre e rispondere a nuove domande, colmando così lacune sulla storia dell’umanità. Reti commerciali, migrazioni, tecniche produttive, molte sono state le scoperte avvenute grazie anche all’intervento scientifico, oltre a fornire strumenti utili al restauro e alla conservazione dei reperti. Nei miei tre anni di dottorato mi sono occupato dell’applicazione dell’analisi in Fluorescenza a Raggi X (XRF) per analizzare campioni metallici e ceramici. Questa tecnica ha il vantaggio di poter essere applicata in maniera non invasiva e non distruttiva su un reperto per ottenere informazioni sulla sua composizione elementare. In particolare, il nostro obiettivo è quello di ottenere informazioni sui diversi strati che compongono un campione. Spesso, infatti, i manufatti presentano una struttura stratificata causata dal passaggio degli anni o dalla natura stessa dell’oggetto, che presenza una serie di decorazioni superficiali. L’impiego di tecniche non invasive permetterebbe quindi di ottenere informazioni più dettagliate anche su campioni al momento inaccessibili, in quanto troppo fragili o troppo preziosi. Lo studio si è quindi avvalso di tecniche a scansione angolare, per cui il segnale di fluorescenza caratteristica dipende sia dalla posizione dell’analita all’interno del campione, sia dalla struttura e composizione dello stesso, sia dalla geometria di analisi. Per valutare l’applicabilità delle tecniche sono stati analizzati tre casi diversi: campioni metallici preparati ad hoc in laboratorio, un campione ceramico, e un campione di lustro. Per i primi due campioni è stata applicata l’XRF a Risoluzione Angolare (AR-XRF) per cui il campione è stato ruotato con uno step angolare inferiore a un grado, e misurato ad ogni step. Nel caso dei campioni metallici i profili misurati sono stati confrontati direttamente con i profili calcolati usando il metodo dei Parametri Fondamentali. Nel caso del campione ceramico invece, sono stati confrontati i rapporti dei profili, in quanto la geometria del campione era piuttosto complessa. Nello studio sui campioni metallici, composti da una doratura depositata su una lamina di rame, è stato possibile calcolare lo spessore dello strato superficiale. Nel caso del campione di Majolica sono invece state studiate le varie decorazioni, valutando così anche diversi limiti della tecnica, in particolar modo nel caso in cui la composizione della decorazione sia simile alla composizione dello strato sottostante, o nel caso in cui avvengano processi di diffusione a lunghe distanze. In casi in cui invece lo spessore della decorazione era limitato e ben separato dallo strato sottostante, è stato possibile ottenere informazioni sua sulla composizione della decorazione che sul suo spessore. Infine, lo studio delle ceramiche lustrate è stato effettuato presso la linea XRF del Sincrotrone di Elettra, impiegando tecniche di analisi in radenza. In questo caso stato possibile solo evidenziare come il nano-strato di nano-particelle di argento, caratteristico di questa tipologia di campioni, sia effettivamente distinguibile applicando queste tecniche, in quanto il profilo di fluorescenza di tale elemento è molto diverso dagli altri. Rimangono comunque dei problemi, legati soprattutto all’analisi dati e all’allineamento che vanno ancora risolti, rendendo necessari ulteriori studi a riguardo.
In the last decades scientific analysis has been deeply employed in the world of cultural heritage, thus, archaeologists and art historians are no more the sole front line workers of this field. Scientists, and science, have joined the team, giving new inputs and tools for the study of historical and archaeological samples, allowing to explore new paths and receive new answers, collecting information otherwise inaccessible on human history and culture. New discoveries have been made on the trade networks, migrations and on the technologies employed; besides, science also gave precious inputs on conservation and restoring procedures, allowing to better preserve fragile and sensitive artifacts. In my three years as a PhD student, I worked on the application of X-Ray Fluorescence (XRF) analysis to analyze ceramic and metal samples. XRF is a non-invasive technique that retrieves the elemental composition of a sample. In particular the aim of my PhD project is to obtain information on the layered structure of an unknown sample, distinguishing and characterizing the different layers. Indeed, artifacts usually concerning the field of Cultural Heritage present a layered structure; sometimes it is due to the presence of alteration layers, other times, instead, the objects are made of different layers from the principle, for example in the case of a glazed ceramic or of a painting. The possibility to get this information in a non-invasive way will give the possibility to analyze objects that are nowadays unattainable, because they cannot be sampled. My project has, thus, focused on the analysis of three kinds of samples employing angular dependent techniques (Angle Resolved-XRF, Grazing Emission-XRF}, Grazing Incidence-XRF}); indeed, the fluorescence signal of an analyte depends on its position inside the sample, on the sample composition and on the geometry of analysis. The chosen specimens allowed to verify the feasibility of this analytical method in an increasing complexity: a gilded laboratory-made sample, a ceramic Majolica sherd, and an Italian renaissance lustered fragment. The first two samples have been analyzed through AR-XRF where the measure is performed while tilting the sample, one spectrum is collected for each tilting angle. In the case of the gilded sample the measured profiles have been compared directly with the calculated profiles employing the Fundamental Parameters method. For the ceramic Majolica sample, instead, we studied the ratio of the profiles, as the sample surface is not flat. In the study of the metallic samples, made of gilded copper plate, we could infer the thickness of the top-layer. While in the case of the Majolica sample, we studied the different decorations, evaluating the limits of the technique, in particular in the case that the top-layer composition is similar to the underling layer, or in the case of a long-range diffusion. Instead, in the case of two well-separate layers we could retrieve information on both the composition and the thickness of the layer. Finally, the study of the lustered ceramic has been carried out at the XRF beamline of the Elettra Synchrotron of Trieste, employing grazing techniques. In this case we could only highlight and distinguish the presence of the silver nanoparticles in the luster nanolayer, which is the peculiar feature of this kind of artifacts. However, there are still many questions left, especially concerning the data analysis and the alignment of the sample, which requires more investigations.

In-situ geotechnical testing of surficial sediment layers in areas of active sediment dynamics can provide essential information about physical and geotechnical variations of sediment properties with regards to active sediment remobilization processes. For example, portable free fall penetrometers (PFFPs) can assist with the detection of mobile sediment layers. They are easy to deploy, and can provide a large spatial coverage in a time- and cost-effective manner. However, they often struggle to provide more detailed information about the properties of mobile sediment layers due to a lack of calibration and validation in existing data sets. Currently, existing sediment samplers often disturb, or ignore the uppermost sediment layers. Simultaneous sediment sampling and geotechnical profiling is needed to fill this gap, and to drive data interpretation forward. A field investigation of surficial sediments was conducted in the wetland waterways of coastal Louisiana in 2014. In-situ tests were conducted using PFFP, and disturbed sediment samples were collected in selected locations. The results allowed us to map changes in sediment strength and stratification, and correlate the geotechnical results to local site characteristics. However, the need for high quality sediment samples for calibration and validation was emphasized by the results. Three different sediment sampler add-on units targeting mobile layers were designed and manufactured based on lessons-learned from the literature. The designs were tested in the laboratory and in the field (Yakutat, Alaska and York River, Virginia) in 2017. The samples were analyzed to understand the influence of different sampler characteristics on collected sample quality, and, to define mobile layer sampler characteristics that enable simultaneous geotechnical testing and the collection of high quality samples. Following field survey campaigns in the York River, Virginia in 2016 allowed to assess surficial sediment layer characteristics and behavior based on a coupled analysis of geotechnical data from in-situ PFFP tests and the sedimentological data collected using box cores and the novel sediment sampler. In summary, novel strategies and instrumentation to carry out simultaneous sediment sampling and geotechnical profiling of seabed surface layers were tested, and new pathways for geotechnical data analysis for the investigation of mobile seabed layers were presented.
PHD

Laikant bulves storame 5 – 6 m storio sluoksnyje, aruode sunku likviduoti susidariusius gedimo židinius. Židinio pašalinimui būtina suintensyvinti ventiliavimą, kad mumifikuoti gedimo židinyje esančius sugedusius gumbus. Tyrimų tikslas - ištirti ventiliuojamo oro paskirstymo dėsningumus bulvių sandėlio sampile ir eksperimentiniame oro paskirstymo stende. Nustatyti oro paskirstymą ventiliuojamame sampile, keičiant skirstomųjų ortakių skaičių, bei ištirti ventiliavimo suintensyvinimo galimybes susidarančias gedimo zonoje. Nustatyta, kad sumažinus atidarytų skirstomųjų ortakių skaičių, galima padvigubinti ventiliavimo intensyvumą likusiuose atidarytuose ortakiuose. Esant atidarytam vienam skirstomajam ortakiui, tiekiamas 8,34 /s oro srautas. Atidarius visus aštuonis ortakius, į kiekvieną ortakį tiekiama tik 3,9 /s oro. Šalia židinio esantys produkcijos sluoksniai bus ventiliuojami žymiai mažesniu ventiliavimo intensyvumu, kas sumažina produkcijos perventiliavimo galimybes likviduojant gedimo židinį sandėlio aruode.
Holding potatoes in a thick 5-6 m layer in the bin it is difficult to eliminate originated hot spots. To remove the source it is necessary to intensify ventilation in order to mummify defective tubers in corruption source. The aim of the research is to investigate the patterns of ventilated air distribution in potato store and distribution of air in an experimental bench. To determine air distribution in ventilated store by changing the number of distribution ducts, and to explore opportunities to intensify ventilation arising in corruption area. It was found that reducing the number of opened distribution ducts the intensity of the ventilation in the remaining opened ducts can be doubled. At the invitation of one ducts supplied 8.34 m3/s air flow. After opening all eight ducts, each duct to be supplied only 3.9 m3/s in air. The layers next to the source will be ventilated with much smaller intensity, which decreases possibility to over ventilate production while eliminating corruption source in the store bin.

Near-infrared optical spectroscopic measurement of samples is an important analytical tool for the determination of properties such as particle size, chromophore composition, and concentration. This information is invaluable for sample assessment in pharmaceutical, agricultural, and environmental areas. However, samples often exhibit significant light scattering, which complicates measurements. This thesis investigates chemometric approaches including power law and component analysis methods to extract useful sample information from data, while simplified instrumentation is developed to facilitate the acquisition of meaningful data. Photon time-of-flight (TOF) techniques allow sample optical properties to be estimated using temporally resolved measurements of short pulses of light. However, highly scattering samples, such as granular powders, are difficult to model. The shape of photon TOF profiles is largely influenced by the properties of these samples. A power law analysis technique was used to study TOF profiles, and a method was developed that could simultaneously determine analyte concentration and particle size. Compared to traditional steady-state measurements, a 3-fold improvement for absorption coefficient and up to a 5-fold improvement for particle size estimates was achieved. This analysis technique is applicable to a variety of areas including pharmaceutics, cosmetics, and chemical production. While methods exist for studying the optical properties of homogeneous optically scattering samples, those containing multiple layers present an interesting challenge for analysis. Spatially resolved measurements from layered samples contain information about the different layers present. However, complications arise when the layer to be probed is non-scattering. In a diffuse reflectance configuration, this type of layer does not provide information in the same way scattering layers do. An analysis technique was developed that allowed the separation of absorption and scattering components for such a layered sample. Accurate estimates of chromophore concentration were attained, even when an overlaying scattering layer had thicknesses that varied between 1 and 8 mm. This method has practical applications for medical, environmental, and industrial applications. A novel self-calibrating technique was developed for the estimation of absorbing species in a non-scattering layer embedded in a non-uniform scattering matrix. Spatially-resolved, steady-state, multispectral data were acquired from an optical head phantom with realistic topographical and optical properties. Experimental and mathematical techniques were developed that allowed accurate estimates of chromophore concentration. A limit of detection corresponding to 5 µL of blood in a volume of 150 ml of CSF was achieved. This system and technique can be useful for noninvasive medical measurements, especially cerebral bleed detection. The work presented in this thesis details key improvements for the spectroscopic analysis of homogenous and layered scattering samples. Each of these advancements represents a further development of our existing spectroscopic knowledge. Of particular interest within the medical community is the self-calibrating work, which can be used to developed noninvasive diagnostic techniques aimed at improving patient care.
La mesure par spectroscopie optique proche infrarouge est un outil d'analyse important pour déterminer les caractéristiques d'un milieu tel la dimension des particules, l'identification de chromophore, et leur concentration. Cette information est de valeur critique pour l'évaluation d'échantillons dans les domaines pharmaceutiques, d'agriculture et environnementaux. Certains échantillons, par contre, diffusent la lumière considérablement, compliquant la mesure. Cette thèse de doctorat examine des méthodes chimiométries comprenant les règles de puissance et les analyses de composante pour extraire de l'information utile d'échantillons à partir des données, alors que l'instrumentation simplifiée est développée pour faciliter l'acquisition des données signicatives. Les techniques utilisant le temps de vol (TDV) des photons permettent de jauger les propriétés visuelles d'échantillons en utilisant la mesure temporale résolue de courtes pulsations de lumière. Il est difficile, par contre, de trouver un modèle pour les milieux à haute diffusion telles les poudres granuleuses. La configuration du profile du TDV photonique est, en grande partie, influencé par les propriétés de l'échantillon. Une analyse des règles de puissance mathématiques fut utilisée afin d'étudier les profiles du TDV, et une méthode fut développée qui pouvait, simultanément, déterminer la concentration des substances sous analyse ainsi que la grandeur des particules. Comparé aux mesures uniformes de fonctionnement traditionnelles, les estimations du coefficient d'absorption futs amélioré par 3 fois et les estimations de grandeurs ont été améliorées par 5 fois. Cette technique d'analyse s'applique à des domaines variés telle la production de produits pharmaceutiques, cosmétiques et chimiques. Quoique des méthodes existent pour étudier les propriétés optiques de substances homogènes à caractères diffusants, les substances ayant de multiples couches présentent un défi d'analyse intéressant. Les mesures faites à des points variés sur l'échantillon à multiples couches donnent de l'information sur les différentes couches présentes. Par contre, la situation se complique lorsque la couche qui doit être sondée n'est pas diffusante. Une couche ayant un facteur de réflexion atténuée, ne révèle pas d'information de la même façon qu'une couche diffusante. Une technique d'analyse fut élaborée qui a permis la séparation des composants d'absorption et diffusants pour ce genre d'échantillon à couche multiple. Des estimations précises de la concentration chromophore ont été obtenues, même lorsque la couche supérieure avait une épaisseur qui variait de 1 à 8 mm. Cette méthode a une utilité pratique dans les domaines médicaux, environnementaux et industriels.Une technique à auto-calibration inusitée fut développée pour estimer les espèces absorbantes dans une couche non diffusante incorporée dans une matrice diffusante dissemblable. Des données multispectrales à point variées, et avec lumière continue ont été obtenues d'une tête optique fantôme ayant des propriétés topographiques et optiques réalistes. Des techniques expérimentales et mathématiques futs développées qui on permit des estimations précises de la concentration chromophore. Une limite de détection correspondant à 5 µL de sang dans un volume de 150 ml de liquide céphalorachidien fut atteinte. Ce système et cette technique peuvent être utiles pour les mesures médicales non invasives, plus précisément pour la détection de saignement cérébrale.Le travail présenté dans cette thèse de doctorat explique les améliorations saillantes pour l'analyse spectroscopique d'échantillons diffusants homogènes et à couches multiples. Chaque amélioration représente une augmentation de nos connaissances de la spectroscopie. La technique à auto-calibration est particulièrement intéressante pour la communauté médicale, car elle peut être utilisée pour développer des techniques non invasives pouvant améliorer le soin de patients.

Combined X-ray powder diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) were used to identify and characterize the clay mineral assemblages in 0.05-0.1 $ mu$m and ${<0.05} mu$m size fractions separated from shales of three depths (4800, 8700-8750, and 12500-12550 ft) from the Reindeer D-27 well in the Beaufort-Mackenzie area, Arctic Canada. Ethylene-glycol solvated samples indicated a two-component mixed-layer I/S system, whereas glycerol solvation suggested an additional high-charge expandable component. Exchange with octylammonium (n$ rm sb c$ = 8) and octadecylammonium (n$ rm sb c$ = 18) ions revealed the presence of five distinct types of layer structures: (1) low-charge smectite-group, (2) high-charge smectite-group or vermiculite, (3) double-layers or rectorite-like, (4) expandable illite, and (5) non-expandable illite. The presence and abundance of each type of layer structure changed with burial depth.
A comparison of untreated and sodium hexametaphosphate-treated ${<0.05} mu$m size fractions revealed modifications to the structure of mixed-layer I/S in both ethylene-glycol solvated and alkylammonium-ion exchanged specimens. Changes in peak position, intensity and breadths are apparent in XRD, and these modifications can also be observed in HRTEM. Lattice-fringe images revealed that pretreatment resulted in: (1) increased abundance of 2:1 layer silicate packets with expanded interlayers, (2) increased R1-ordered sequences, and (3) thinner packets of non-expanded illite interlayers. The use of sodium hexametaphosphate as a peptizer alters the interlayers and modifies the stacking arrangement of the layer structures. If the primary structure is altered, the disruption may be irreversible.
It is evident therefore, that reliable ratio determination between expandable and non-expandable components in mixed-layer I/S is dependent on characterizing all the components and resolving the effects of chemical pretreatment.

The prevalence of antimicrobial residues in table eggs produced in Khartoum State, Sudan was estimated and determined. All available producing layer farms in the state were sampled in April, June and August 2008. For each layer house three egg samples were randomly collected to increase the sensitivity of antimicrobial residue screening test detectability. In total, 933 egg samples were analyzed, collected from 175 layer farms (335 layer houses) in three periods of collection. An in-house residue detection test using Geobacillus stearothermophillus var calidolactis was the analytical procedure used for the analysis. Data were analysed using Survey Toolbox to calculate the true prevalence and confidence intervals. The proportion of layer farms with antimicrobial residues in April, June and August was 61.1%, 60.2% and 68.7% respectively. The proportion of layer houses affected in April, June and August were 56.0%, 54.1% and 57.1% respectively. The results showed insignificant variation among the three periods of the surveillance (p = 0.57). A census covering all three localities of the state (Khartoum, Bahry and Omdurman) was carried out in late 2007 and early 2008. Data were recorded on areas where farms occur, number of houses per farm, total capacity of birds and farming systems. The census showed that there were 252 layer farms in the state distributed in 31 different areas with a total population of 2 221 800 birds. A structured questionnaire survey was carried out in April 2008 in the state, to assess and collect data on risk factors associated with the presence of antimicrobial residues in table eggs. The questionnaire investigated antibiotic usage patterns for each layer farm as well as the basic knowledge and understanding of farmers about public health concerns associated with antibiotic use in food producing animals. Questions were closed ended and data was obtained through direct interviews with farm owners and managers. Descriptive statistical analysis was carried out on the information captured; calculating frequencies, graphs and measures of association, using the EpiInfo™ statistical package. Ninety two farms were surveyed 98% of which comprised open-sided houses. It was found that 48.9% of the farms surveyed were on antibiotic treatment when the survey was conducted, while 58.7% of the farms had used antibiotics within the last three months. There was a significant association between having disease on the farm and using antibiotics (P<0.001). The study showed that there is a serious lack of knowledge about the dangers of using antibiotics in animals and their potential impact on human health. In addition, Sudan lacks any type of formal control of veterinary drugs in terms of legislated residue limits or monitoring and surveillance programmes. This leads the authors to the conclusion that all Sudanese consumers are at risk for ARs in eggs.
Dissertation (MSc)--University of Pretoria, 2010.
Production Animal Studies
unrestricted

The strongly time variant flow in an incompressible, turbulent junction vortex formed at the base of a streamlined cylinder with a circular leading edge placed normal to a flat surface was investigated. The investigation centered around spectral analysis and time resolved measurements of the velocity fluctuations to characterize the time variant flow on the plane of symmetry. All the measurements were performed with a two-color, two-component, frequency shifted laser Doppler velocimeter. Spectral analysis methods for randomly sampled data occurring from the LDV were evaluated under various simulated and real flow situations. The real flow situations studied were the vortex shedding flow behind a cylinder and the two-dimensional turbulent boundary layer. The spectral estimates obtained from the discretized lag product method were found to be better than those obtained from the direct transform method. It was found that the exact lag product method does not offer significant improvements in the spectral estimates to offset its computational slowness. The mean velocity vectors in the junction vortex showed a single vortex on the plane of symmetry and a singular separation point upstream of the cylinder. The time resolved measurements showed the instantaneous separation point on the plane of symmetry to be randomly oscillating between two limits. Maximum possible excursions of the junction vortex position and size were also obtained form the time resolved measurements. The turbulence intensities in the junction vortex were found to be at least two to three times higher than typical two-dimensional boundary layer values. The histograms of instantaneous velocity fluctuations deviated from the expected Gaussian distributions and were found to have multiple peaks. The spectral content of the junction vortex flow was investigated. The overall character of the junction vortex flow was found to be similar to a two-dimensional turbulent boundary layer, with greater amplification perceived in the lower frequencies relative to the higher frequencies. The spectra at locations above the time mean center of the junction vortex showed distinct peaks around 20-30 Hz, unlike boundary layer flows.
Ph. D.

Perfect slice sampling is a method to turn Markov Chain Monte Carlo (MCMC) samplers into exact generators for independent random variates. The originally proposed method is rather slow and thus several improvements have been suggested. However, two of them are erroneous. In this article we give a short introduction to perfect slice sampling, point out incorrect methods, and give a new improved version of the original algorithm. (author's abstract)
Series: Preprint Series / Department of Applied Statistics and Data Processing

The first chapter proposes multifractal analysis to measure inhomogeneity of regularity of 1H-NMR spectrum using wavelet-based multifractal tools. The geometric summaries of multifractal spectrum are informative summaries, and as such employed to discriminate 1H-NMR spectra associated with different treatments. The methodology is applied to evaluate the effect of sulfur amino acids. The second part of this thesis provides essential materials for understanding engineering background of a nano-particle fabrication process. The third chapter introduces a constrained random effect model. Since there are certain combinations of process variables resulting to unproductive process outcomes, a logistic model is used to characterize such a process behavior. For the cases with productive outcomes a normal regression serves the second part of the model. Additionally, random-effects are included in both logistics and normal regression models to describe the potential spatial correlation among data. This chapter researches a way to approximate the likelihood function and to find estimates for maximizing the approximated likelihood. The last chapter presents a method to decide the sample size under multi-layer system. The multi-layer is a series of layers, which become smaller and smaller. Our focus is to decide the sample size in each layer. The sample size decision has several objectives, and the most important purpose is the sample size should be enough to give a right direction to the next layer. Specifically, the bottom layer, which is the smallest neighborhood around the optimum, should meet the tolerance requirement. Performing the hypothesis test of whether the next layer includes the optimum gives the required sample size.

ALM-based production of Titanium components shows great promise in supplying cost-effective products within industries such as energy, chemical processing and aerospace. In common for all is high quality demands. This necessitates extensive research into the intricacies of this production process. Complex microstructures comprised of columnar remnants of directionally solidified &#946;-Titanium, with interior inhabited by colonies of finer &#945;-plate structures were found in samples produced by layered plasma welding of alloy Ti-6Al-4V. Utilising the powerful characterisation tool of in-situ tensile tests combined with EBSD analysis allowed qualitative correlation between microstructural features and deformation characteristics. Non-uniform deformation occurs due to a strong variation of strain response between colonies. Prismatic and basal slip systems are active, with the prismatic systems contributing to the most severe deformation through coarse, widely spaced slip bands. Certain colonies behave as microstructural units, with easy slip transmission across the entire colony. Other colonies show significant deformation mismatch, with local build up of strain gradients and stress concentration. Segmentation occurs due to the growth morphology imposed by the columnar grains. Tensile tests perpendicular to columnar structures reveal strong deformation localization. Connections are made between the peculiarities of the production process and the observed microstructure and deformation mechanisms.

A aplicação do processo de fotoeletrocatálise à eliminação de interferentes orgânicos em baixa concentração na eletroanálise de metais foi abordada tomando o quelato Cu(II)-EDTA como sistema modelo e o restabelecimento da onda voltamétrica do cobre como indicador de efetividade. Desenvolveram-se células eletroquímicas de camada delgada (espessura de 600 micrômetros) nas quais alguns microlitros de amostra são tratados sobre um eletrodo modificado com TiO2 (tipo P25, rico em anatase), cuja superfície é irradiada através de uma janela por um LED (370 nm). Foram construídos e avaliados os seguintes eletrodos: pasta de carbono, TiO2 e óleo parafínico (CPE-TiO2), compósitos de grafite, TiO2 e adesivo epóxi ou de silicone e ouro com oclusão de TiO2 por eletrodeposição. Estudo do efeito de parâmetros como potencial aplicado ao eletrodo, composição do eletrólito e concentração de EDTA sobre a fotocorrente permitiu selecionar condições de trabalho e estabelecer algumas correlações. Por exemplo, observou-se linearidade entre a fotocorrente e a concentração de EDTA até 1,0 mmol/L, aparente limite superior do controle difusional do processo para potência radiante aplicada, acima do qual, a cinética de oxidação passa a sobrepujar o transporte no controle da velocidade de reação. O restabelecimento pleno da onda de Cu(II) 1,0 mmol.L-1 foi observado após a irradiação por 10 min quando a concentração de EDTA não excedia 0,94 mmol.L-1. Descobriu-se um procedimento mais rápido que consiste na aplicação do tratamento fotoeletrocatalítico simultâneo ao registro de voltamogramas cíclicos repetitivos (eletrodo de Au-TiO2, 0,3 a 0,7 V vs. Ag/AgCl, 100 mV.s-1). Após o sexto ciclo, a altura do pico de redissolução anódica do Cu (reduzido durante a varredura no sentido negativo) estabiliza, permitindo a quantificação sem etapa prévia de abertura.
The photoelectrocatalysis process was investigated for the elimination of organic compounds interference on the electroanalysis of trace metals. Cu(II)-EDTA chelate was chosen as model system and the recovery of copper voltammetric peak, as effectiveness indicator. Thin layer cells (thickness of 600 micrometers) were designed for the treatment of some microliters of sample by irradiation (370 nm LED) of an electrode modified with TiO2 (P25, anatase rich). The following modified electrodes were prepared and evaluated: carbon paste with TiO2 and paraffin oil (CPE-TiO2), composites of graphite, TiO2 and epoxy or silicone binders and TiO2 occluded in electrodeposited gold on a gold substrate. The effect of parameters like potential bias, electrolyte composition and EDTA concentration on the photocurrent was evaluated to setup working conditions. Some correlations were observed, e.g., a linear dependence between photocurrent and EDTA concentration up to 1.0 mmol/L. For the irradiance applied, this concentration is possibly the upper limit of operation diffusion transport control, above which, the kinetics of the oxidation at the TiO2 modified electrode becomes the controlling process. For EDTA concentrations not exceeding 0.94 mmol.L-1, full recovery of 1.0 mmol.L-1 Cu(II) voltammetric peaks was observed after 10 min of irradiation. A faster procedure was discovered and consists in recording repetitive cyclic voltammograms (Au-TiO2 electrode, 0,3 to 0,7 V vs. Ag/AgCl scans, 100 mV.s-1) simultaneously with continuous irradiation. After the sixth cycle, the copper anodic stripping peak height stabilizes allowing quantification without previous sample pre-treatment step.

Le complexe mafique–ultramafique lité Yacouba est intrusif au sein des granulites gneissiques du domaine archéen de Man (3,6-2,78 Ga) dans la région de Biankouma-Sipilou (ouest de la Côte d'Ivoire). Dans le secteur de Samapleu, il est composé de trois entités ; dépôt principal de Samapleu (SM), l’Extension 1 de Samapleu (E1) et l’occurrence de Yorodougou (Yo). Il comprend des horizons de webstérites, péridotites, chromitites, norites, gabbro-norites. Ces horizons (épaisseur cumulée de 80 à 200 m) sont inclinés de 70 à 80° vers le SE ; présentent une zonation concentrique, qui sont autant de caractéristiques d’un dyke ; un enracinement à plus de 600 m à partir de la surface avec une jonction des intrusions (SM, E1) plus en profondeur. Les contacts avec l’encaissant gneissique (localement site E1) sont marqués par une zone hybride (condition P = 7,5±1Kbar et T = 850°C ± 100°C) interprétées comme le résultat d'un métamorphisme de contact lors de la mise en place de l’intrusion en base de croûte à environ 22 km de profondeur. Les gneiss et granulites du socle, tout comme les faciès de la zone hybride, préservent des âges archéens (~2,78 Ga, U-Pb sur zircon). Des cristaux de rutile observés dans la zone hybride révèlent un âge U-Pb de 2,09 Ga interprété comme l'âge du métamorphisme de contact et donc de la mise en place de l'intrusion.La minéralisation en Ni-Cu (essentiellement disséminée avec des veines sulfurées subverticales semi-massives à massives) est composée de pentlandite, chalcopyrite, pyrrhotite, rarement pyrite. La texture des sulfures varie de matricielle, en filets, en gouttelettes, ou brèchique. Les réserves estimées des dépôts de Samapleu (SM et E1) font plus de 40 millions de tonnes à une teneur moyenne de 0,25% Ni et 0,22% Cu dans la partie supérieure des intrusions (Sama Nickel-CI, Août 2013). Des MGP riches en palladium (Pd) sont associés aux sulfures et plusieurs bandelettes de chromite sont également présentes. Ces observations suggèrent un liquide sulfuré immiscible formé à partir du liquide silicaté initial consécutivement à la saturation en soufre du système. Ces sulfures d’origine essentiellement mantellique ont été probablement formés par injection de plusieurs magmas. Cependant une partie de ces sulfures aurait pu se former par l’assimilation des roches granulitiques encaissantes.La composition du liquide parent révèle une composition de basalte à forte teneur en MgO et faible teneur en Ti et suggère que les intrusions de Samapleu se sont formées par fusion du manteau supérieur sous l’influence d'un panache mantellique. Ainsi, lors de leurs remontées, le magma a assimilé les roches granulites encaissantes environnantes
The Yacouba layered complex intrudes the archean (3.6-2.78 Ga) Man field in the Biankouma-Sipilou area, western Ivory Coast. In Samapleu area, the complex is composed of three entities; Samapleu Main (SM); Samapleu Extension 1 (E1) and Yorodougou (Yo). It includes websterites, peridotites, chromitites, norites, gabbro-norites horizons. These horizons (total thickness of 80 to 200 m) inclined at 70-80° to the SE; arranged symmetrically with mafic layers at the center and ultramafic layers at both margins, are features of a dyke ; show a root more than 600 m from the surface with a junction intrusion (SM, E1) in more depth.At the E1 site, contacts of intrusions with the country rock gneiss are characterized by a hybrid zone (condition P = 7.5±1Kbar and T = 850°C ± 100°C) attributed to contact metamorphism during intrusion of the complex in the lower crust at a depth of about 22 km. Zircons in country rock gneisses and granulites, as well as in the hybrid facies, yield archean ages of ~ 2.78 Ga. Rutiles in the hybrid zone give a U-Pb age of 2.09 Ga, which is interpreted as the age of contact metamorphism and emplacement of the intrusion.The Ni-Cu mineralization (disseminated mainly with subvertical and semi-massive to massive sulfide veins) is composed of pentlandite, chalcopyrite, pyrrhotite and rare pyrite. The SM and E1 sites contain Ni and Cu sulfide deposit with reserves estimated as more than 40 million tons grading 0.25% Ni and 0.22% Cu in the upper portion (Sama Nickel-CI, August 2013). The sulfide textures range from matrix ore, net-textured, droplets or breccia textures. Zones enriched in PGM, particularly Pd, are associated with the sulfides and several chromite bands are also present. These observations suggest that an immiscible sulfide liquid formed from a parental silicate liquid and percolated through the crystal pile. These sulfides mainly mantle origin were probably formed by injecting several magmas. However few of these sulfides may have formed by the assimilation of country rocks.The parental melt composition has a basalt rich MgO and low Ti and suggest Samapleu intrusions were formed by melting of the upper mantle under the influence of a mantle plume. Thus, during its ascent, magma has assimilated the granulites country rocks

Air pollutants pose a high risk for humans, and the environment, and this pollution is one of the major environmental problems facing modern society. Active air sampling is the technique that has been traditionally used to monitor nonpolar aromatic air pollutants. However, active high volume samplers (HiVols) require a power supply, maintenance and specialist operators, and the equipment is often expensive. Thus, there is a need to develop new, less complicated sampling techniques that can increase the monitoring frequency, the geographical distribution of the measurements, and the number of sites used in air monitoring programs. In the work underlying this thesis, the use of semipermeable membrane devices (SPMDs) as tools for monitoring gas phase concentrations of nonpolar aromatic compound was evaluated using the compound classes polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs) and nitrated PAHs (nitro-PAHs) as test compounds.

High wind-speeds increased the uptake and release in SPMDs of PAHs and PCBs with log K_OA values > 7.9, demonstrating that the uptake of most nonpolar aromatic compounds is controlled by the boundary layer at the membrane-air interface. The use of a metal umbrella to shelter the SPMDs decreased the uptake of PAHs and PCBs by 38 and 55 percent, respectively, at high wind/turbulence, and thus reduced the wind effect. Further, the use of performance reference compounds (PRCs) to assess the site effect of wind on the uptake in SPMDs reduced the between-site differences to less than 50 percent from as much as three times differences in uptake of PCBs and PAHs. However, analytical interferences reduced the precision of some PRCs, showing the importance of using robust analytical quality control.

SPMDs were shown to be efficient samplers of gas phase nonpolar aromatic compounds, and were able to determine local, continental and indoor spatial distributions of PAHs, alkyl- PAHs and nitro-PAHs. In addition, the use of the SPMDs, which do not require electricity, made sampling possible at remote/rural areas where the infrastructure was limited. SPMDs were also used to determine the source of PAH pollution, and different approaches were discussed. Finally, SPMDs were used to estimate the importance of the gas phase exposure route to the uptake of PAHs in plants. The results demonstrate that SPMDs have several advantages compared with HiVols, including integrative capacity over long times, reduced costs, and no need of special operators, maintenance or power supply for sampling. However, calibration data of SPMDs in air are limited, and spatial differences are often only semi-quantitatively determined by comparing amounts and profiles in the SPMDs, which have limited their use in air monitoring programs. In future work, it is therefore important that SPMDs are properly sheltered, PRCs are used in the sampling protocols, and that calibrated sampling rate data, or the SPMD-air partition data, of specific compounds are further developed to make determination of time weighted average (TWA) concentrations possible.

PIXE (Particle Induced X-ray Emission) et PIGE (Particle Induced Gamma-ray Emission) sont des méthodes d’analyse par faisceau d’ions, multiélémentaires et non destructives. Elles sont basées sur la détection des rayons X et gamma caractéristiques émis suite à l’interaction de particules chargées avec la matière. La méthode PIXE permet de quantifier les éléments de numéro atomique Z>11 avec une limite de détection au niveau du μg/g (ppm). Les rayons X émis par les éléments légers (Z<11) sont fortement atténués par la matière, limitant la sensibilité de PIXE pour cette gamme de numéro atomique. Ces éléments peuvent légers être analysés, simultanément, par la méthode PIGE. Un des nombreux avantages de la méthode PIXE/PIGE est sa capacité à pouvoir effectuer différentes analyses (cartographie des concentrations, analyse en profondeur, objets précieux). Il est possible d’analyser des échantillons aussi bien homogènes que non homogènes. La méthode PIXE à haute énergie a été développée au cyclotron ARRONAX avec des faisceaux de particules pouvant atteindre 70 MeV. La technique PIXE à haute énergie permet, notamment, l’analyse d’échantillons épais et limite les risques d’endommagement. Premièrement la plateforme PIXE/PIGE à haute énergie est décrite. Ensuite une étude de la méthode PIGE à haute énergie ainsi que la mise en place d’un protocole de mesure de sections efficaces sont présentées. Pour finir les méthodes mises en place ainsi que les résultats obtenus lors de l’analyse de plusieurs types d’échantillons non homogènes (multicouches et granulaires) sont présentés et discutés
Particle Induced X-ray Emission (PIXE) and Particle Induced Gamma-ray Emission (PIGE) are multi-elemental and non-destructives techniques. They are based on the detection of characteristic X-ray and gamma emission induced by the interaction of accelerated charged particles with matter. Elements with an atomic number Z> 11 can be quantified reaching a limit of detection in the order of μg/g (ppm). X-rays from light elements are strongly attenuate by matter. Therefore, PIXE shows little sensitivity for lights elements. Those elements are analyzed simultaneously using PIGE. One of the benefits of PIXE/PIGE is its ability to perform analysis with different requirement (elemental concentration mapping, in-depth analysis, valuable objects). Homogeneous and non-homogenous samples can be studied thanks to PIXE/PIGE. High energy PIXE (HEPIXE) has been developed at the ARRONAX cyclotron using particles beams up to 70 MeV. Thus analysis of thick samples is achievable using HEPIXE. Using high energy beams can also reduce the risk of damaging the sample. First of all, the high energy PIXE/PIGE platform develop at ARRONAX is described. Then the results given by high energy PIGE analysis and the experimental procedure for gamma emission cross section measurements are discussed. Finally, the methods developed and the results obtained during the analysis of inhomogeneous samples (multi-layer and granular samples) are presented and discussed

Tato práce se zabývá možnostmi kvantitativního zobrazování ve skenovacím (transmisním) elektronovém mikroskopu (S|T|EM) společně s jejich korelativní aplikací. Práce začíná popisem metody kvantitativního STEM (qSTEM), kde lze stanovenou lokální tloušťku vzorku dát do spojitosti s ozářenou dávkou, a vytvořit tak studii úbytku hmoty. Tato metoda byla použita při studiu ultratenkých řezů zalévací epoxidové pryskyřice za různých podmínek (stáří, teplota, kontrastování, čištění pomocí plazmy, pokrytí uhlíkem, proud ve svazku). V rámci této části jsou diskutovány a demonstrovány možnosti kalibračního procesu detektoru, nezbytné pozadí Monte Carlo simulací elektronového rozptylu a dosažitelná přesnost metody. Metoda je pak rozšířena pro použití detektoru zpětně odražených elektronů (BSE), kde byla postulována, vyvinuta a testována nová kalibrační technika založená na odrazu primárního svazku na elektronovém zrcadle. Testovací vzorky byly různě tenké vrstvy v tloušťkách mezi 1 až 25 nm. Použití detektoru BSE přináší možnost měřit tloušťku nejen elektronově průhledných vzorků jako v případě qSTEM, ale také tenkých vrstev na substrátech - qBSE. Obě výše uvedené metody (qSTEM a qBSE) jsou založeny na intenzitě zaznamenaného obrazu, a to přináší komplikaci, protože vyžadují správnou kalibraci detektoru, kde jen malý posun úrovně základního signálu způsobí významnou změnu výsledků. Tato nedostatečnost byla překonána v případě qSTEM použitím nejpravděpodobnějšího úhlu rozptylu (zachyceného pixelovaným STEM detektorem), namísto integrální intenzity obrazu zachycené prstencovým segmentem detektoru STEM. Výhodou této metody je její použitelnost i na data, která nebyla předem zamýšlena pro využití qSTEM, protože pro aplikaci metody nejsou potřeba žádné zvláštní předchozí kroky. Nevýhodou je omezený rozsah detekovatelných tlouštěk vzorku způsobený absencí píku v závislosti signálu na úhlu rozptylu. Obecně platí, že oblast s malou tloušťkou je neměřitelná stejně tak jako tloušťka příliš silná (použitelný rozsah je pro latex 185 - 1 000 nm; rozsah je daný geometrií detekce a velikostí pixelů). Navíc jsou v práci prezentovány korelativní aplikace konvenčních a komerčně dostupných kvantitativních technik katodoluminiscence (CL) a rentgenové energiově disperzní spektroskopie (EDX) spolu s vysokorozlišovacími obrazy vytvořenými pomocí sekundárních a prošlých elektronů.

Est-il possible de démontrer un théorème prouvant que l’accès aux données confidentielles d’un utilisateur d’un service Web (tel que GMail) nécessite la connaissance de son mot de passe, en supposant certaines hypothèses sur ce qu’un attaquant est incapable de faire (par exemple, casser des primitives cryptographiques ou accéder directement aux bases de données de Google), sans toutefois le restreindre au point d’exclure des attaques possibles en pratique?Il existe plusieurs facteurs spécifiques aux protocoles du Web qui rendent impossible une application directe des méthodes et outils existants issus du domaine de l’analyse des protocoles cryptographiques.Tout d’abord, les capacités d’un attaquant sur le Web vont largement au-delà de la simple manipulation des messages échangés entre le client et le serveur sur le réseau. Par exemple, il est tout à fait possible (et même fréquent en pratique) que l’utilisateur ait dans son navigateur un onglet contenant un site contrôlé par l’adversaire pendant qu’il se connecte à sa messagerie (par exemple, via une bannière publicitaire) ; cet onglet est, comme n’importe quel autre site, capable de provoquer l’envoi de requêtes arbitraires vers le serveur de GMail, bien que la politique d’isolation des pages du navigateur empêche la lecture directe de la réponse à ces requêtes. De plus, la procédure pour se connecter à GMail implique un empilement complexe de protocoles : tout d’abord, un canal chiffré, et dont le serveur est authentifié, est établi avec le protocole TLS ; puis, une session HTTP est créée en utilisant un cookie ; enfin, le navigateur exécute le code JavaScript retourné par le client, qui se charge de demander son mot de passe à l’utilisateur.Enfin, même en imaginant que la conception de ce système soit sûre, il suffit d’une erreur minime de programmation (par exemple, une simple instruction goto mal placée) pour que la sécurité de l’ensemble de l’édifice s’effondre.Le but de cette thèse est de bâtir un ensemble d’outils et de librairies permettant de programmer et d’analyser formellement de manière compositionelle la sécurité d’applicationsWeb confrontées à un modère plausible des capacités actuelles d’un attaquant sur le Web. Dans cette optique, nous étudions la conception des divers protocoles utilisés à chaque niveau de l’infrastructure du Web (TLS, X.509, HTTP, HTML, JavaScript) et évaluons leurs compositions respectives. Nous nous intéressons aussi aux implémentations existantes et en créons de nouvelles que nous prouvons correctes afin de servir de référence lors de comparaisons. Nos travaux mettent au jour un grand nombre de vulnérabilités aussi bien dans les protocoles que dans leurs implémentations, ainsi que dans les navigateurs, serveurs, et sites internet ; plusieurs de ces failles ont été reconnues d’importance critiques. Enfin, ces découvertes ont eu une influence sur les versions actuelles et futures du protocole TLS
As ever more private user data gets stored on the Web, ensuring proper protection of this data (in particular when it transits through untrusted networks, or when it is accessed by the user from her browser) becomes increasingly critical. However, in order to formally prove that, for instance, email from GMail can only be accessed by knowing the user’s password, assuming some reasonable set of assumptions about what an attacker cannot do (e.g. he cannot break AES encryption), one must precisely understand the security properties of many complex protocols and standards (including DNS, TLS, X.509, HTTP, HTML,JavaScript), and more importantly, the composite security goals of the complete Web stack.In addition to this compositional security challenge, onemust account for the powerful additional attacker capabilities that are specific to the Web, besides the usual tampering of network messages. For instance, a user may browse a malicious pages while keeping an active GMail session in a tab; this page is allowed to trigger arbitrary, implicitly authenticated requests to GMail using JavaScript (even though the isolation policy of the browser may prevent it from reading the response). An attacker may also inject himself into honest page (for instance, as a malicious advertising script, or exploiting a data sanitization flaw), get the user to click bad links, or try to impersonate other pages.Besides the attacker, the protocols and applications are themselves a lot more complex than typical examples from the protocol analysis literature. Logging into GMail already requires multiple TLS sessions and HTTP requests between (at least) three principals, representing dozens of atomic messages. Hence, ad hoc models and hand written proofs do not scale to the complexity of Web protocols, mandating the use of advanced verification automation and modeling tools.Lastly, even assuming that the design of GMail is indeed secure against such an attacker, any single programming bug may completely undermine the security of the whole system. Therefore, in addition to modeling protocols based on their specification, it is necessary to evaluate implementations in order to achieve practical security.The goal of this thesis is to develop new tools and methods that can serve as the foundation towards an extensive compositional Web security analysis framework that could be used to implement and formally verify applications against a reasonably extensive model of attacker capabilities on the Web. To this end, we investigate the design of Web protocols at various levels (TLS, HTTP, HTML, JavaScript) and evaluate their composition using a broad range of formal methods, including symbolic protocol models, type systems, model extraction, and type-based program verification. We also analyze current implementations and develop some new verified versions to run tests against. We uncover a broad range of vulnerabilities in protocols and their implementations, and propose countermeasures that we formally verify, some of which have been implemented in browsers and by various websites. For instance, the Triple Handshake attack we discovered required a protocol fix (RFC 7627), and influenced the design of the new version 1.3 of the TLS protocol

Proučavane su koroziona postojanost i tendencija lepljenja različitihmaterijala u kontaktu sa tečnom Al–Si–Cu legurom. Ispitivanjem suobuhvaćeni čelik za rad na toplo, plazma nitrirani čelik i dupleksslojevi sa CrN, TiAlN, TiAlSiN i CrAlN prevlakama, različitog nivoapovršinske hrapavosti. Za ispitivanja pomenutih fenomenaprimenjena je metoda izvlačenja, koja je unapređena kako bi se povećalenjena tačnost i verodostojnost simulacije procesa livenja. Korozioniefekti su pojačani tako što su uzorci osim kratkog kontakta sa odlivkomzadržavani i u dužim periodima u kontaktu sa tečnom legurom (5 i 20min). Uprkos opštim stavovima, za ispitivane materijale jeustanovljeno da su sile izvlačenja uzoraka iz Al–Si–Cu odlivakanezavisne od njihovog hemijskog sastava. Uticaj hrapavosti je izraženkod uzoraka sa prevlakama kod kojih pri smanjenju hrapavosti dolazi dopovećanja sile izvlačenja. Sve ispitane prevlake su sklone mehaničkomlepljenju Al–Si–Cu legure za svoje površine, ali sa aspekta korozije utečnom metalu značajno prevazilaze performanse čelika i plazmanitriranog sloja. Duži kontakt livene legure sa površinama prevlakauzrokovao je niže vrednosti sila izvlačenja, što je posledicaoksidacije površina prevlaka. Ustanovljeno je da su ispitivaneprevlake inertne ka tečnoj leguri aluminijuma. Međutim, dolazi dooksidacije i korozije materijala podloge kroz greške rasta koje suprisutne u prevlakama. Stečena znanja o identifikovanimmehanizmima habanja i propadanja zaštitnih slojeva prevlakaposlužiće daljem razvoju dupleks slojeva namenjenih za zaštitu alataza livenje pod pritiskom.
Corrosion resistance and soldering tendency of different materials in moltenAl–Si–Cu alloy were studied. Hot-working tool steel, plasma nitrided steel andduplex layers with CrN, TiAlN, TiAlSiN and CrAlN top coatings, which wereproduced to various degree of surface roughness, were covered by the study.An ejection test was employed for investigation of the concerned phenomena.The ejection test was improved in order to increase its accuracy and thereliability of process simulation. Samples were examined in both short andextended periods of contact (5 and 20 min) with liquid casting. Castingsolidification was extended in order to intensify the corrosion effects. Contraryto common findings, it was found that the ejection force of the investigatedmaterials does not depend on their chemical composition. For the coatedsamples, a pronounced dependence of the ejection force on the surfaceroughness was found. The ejection force increases with decrease in surfaceroughness. All investigated coatings are prone to mechanical soldering by Al–Si–Cu alloy. Still, their corrosion resistance substantially exceeds the corrosionresistance of steel and plasma nitrided layer. Longer exposure of coatedsamples to cast alloy induced lower ejection forces, which is a consequenceof coatings oxidation. It was found that the investigated coatings are inert toliquid aluminium. However, the underlying material undergoes oxidation andcorrosion through coating growth defects. The findings concerning the wearmechanisms of protective layers support further development of duplex layersintended for die casting tools protection.

In der vorliegenden Arbeit wird erstmals das QQDS-Magnetspektrometer für die höchstauflösende Ionenstrahlanalytik leichter Elemente am Helmholtz-Zentrum Dresden-Rossendorf umfassend vorgestellt. Zusätzlich werden sowohl alle auf die Analytik Einfluss nehmenden Parameter untersucht als auch Methoden und Modelle vorgestellt, wie deren Einfluss vermieden oder rechnerisch kompensiert werden kann. Die Schwerpunkte dieser Arbeit gliedern sich in fünf Bereiche. Der Erste ist der Aufbau und die Inbetriebnahme des QQDS-Magnetspektrometers, der zugehörige Streukammer mit allen Peripheriegeräten und des eigens für die höchstauflösende elastische Rückstoßanalyse entwickelten Detektors. Sowohl das umgebaute Spektrometer als auch der im Rahmen dieser Arbeit gebaute Detektor wurden speziell an experimentelle Bedingungen für die höchstauflösende Ionenstrahlanalytik leichter Elemente angepasst und erstmalig auf einen routinemäßigen Einsatz hin getestet. Der Detektor besteht aus zwei Komponenten. Zum einen befindet sich am hinteren Ende des Detektors eine Bragg-Ionisationskammer, die zur Teilchenidentifikation genutzt wird. Zum anderen dient ein Proportionalzähler, der eine Hochwiderstandsanode besitzt und direkt hinter dem Eintrittsfenster montiert ist, zur Teilchenpositionsbestimmung im Detektor. Die folgenden zwei Schwerpunkte beinhalten grundlegende Untersuchungen zur Ionen-Festkörper-Wechselwirkung. Durch die Verwendung eines Magnetspektrometers ist die Messung der Ladungszustandsverteilung der herausgestreuten Teilchen direkt nach einem binären Stoß sowohl möglich als auch für die Analyse notwendig. Aus diesem Grund werden zum einen die Ladungszustände gemessen und zum anderen mit existierenden Modellen verglichen. Außerdem wird ein eigens entwickeltes Modell vorgestellt und erstmals im Rahmen dieser Arbeit angewendet, welches den ladungszustandsabhängigen Energieverlust bei der Tiefenprofilierung berücksichtigt. Es wird gezeigt, dass ohne die Anwendung dieses Modells die Tiefenprofile nicht mit den quantitativen Messungen mittels konventioneller Ionenstrahlanalytikmethoden und mit der Dickenmessung mittels Transmissionselektronenmikroskopie übereinstimmen, und damit falsche Werte liefern würden. Der zweite für die Thematik wesentliche Aspekt der Ionen-Festkörper-Wechselwirkung, sind die Probenschäden und -modifikationen, die während einer Schwerionen-bestrahlung auftreten. Dabei wird gezeigt, dass bei den hier verwendeten Energien sowohl elektronisches Sputtern als auch elektronisch verursachtes Grenzflächendurchmischen eintreten. Das elektronische Sputtern kann durch geeignete Strahlparameter für die meisten Proben ausreichend minimiert werden. Dagegen ist der Einfluss der Grenzflächendurchmischung meist signifikant, so dass dieser analysiert und in der Auswertung berücksichtigt werden muss. Schlussfolgernd aus diesen Untersuchungen ergibt sich für die höchstauflösende Ionenstrahlanalytik leichter Elemente am Rossendorfer 5-MV Tandembeschleuniger, dass die geeignetsten Primärionen Chlor mit einer Energie von 20 MeV sind. In Einzelfällen, wie zum Beispiel der Analyse von Bor, muss die Energie jedoch auf 6,5 MeV reduziert werden, um das elektronische Sputtern bei der notwendigen Fluenz unterhalb der Nachweisgrenze zu halten. Der vierte Schwerpunkt ist die Untersuchung von sowohl qualitativen als auch quantitativen Einflüssen bestimmter Probeneigenschaften, wie beispielsweise Oberflächenrauheit, auf die Form des gemessenen Energiespektrums beziehungsweise auf das analysierte Tiefenprofil. Die Kenntnis der Rauheit einer Probe an der Oberfläche und an den Grenzflächen ist für die Analytik unabdingbar. Als Resultat der genannten Betrachtungen werden die Einflüsse von Probeneigenschaften und Ionen-Festkörper-Wechselwirkungen auf die Energie- beziehungsweise Tiefenauflösung des Gesamtsystems beschrieben, berechnet und mit der konventionellen Ionenstrahlanalytik verglichen. Die Möglichkeiten der höchstauflösenden Ionenstrahlanalytik werden zudem mit den von anderen Gruppen veröffentlichten Komplementärmethoden gegenübergestellt. Der fünfte und letzte Schwerpunkt ist die Analytik leichter Elemente in ultradünnen Schichten unter Berücksichtigung aller in dieser Arbeit vorgestellten Modelle, wie die Reduzierung des Einflusses von Strahlschäden oder die Quantifizierung der Elemente im dynamischen Ladungszustandsnichtgleichgewicht. Es wird die Tiefenprofilierung von Mehrschichtsystemen, bestehend aus SiO2-Si3N4Ox-SiO2 auf Silizium, von Ultra-Shallow-Junction Bor-Implantationsprofilen und von ultradünnen Oxidschichten, wie zum Beispiel High-k-Materialien, demonstriert
In this thesis the QQDS magnetic spectrometer that is used for high resolution ion beam analysis (IBA) of light elements at the Helmholtz-Zentrum Dresden-Rossendorf is presented for the first time. In addition all parameters are investigated that influence the analysis. Methods and models are presented with which the effects can be minimised or calculated. There are five focal points of this thesis. The first point is the construction and commissioning of the QQDS magnetic spectrometer, the corresponding scattering chamber with all the peripherals and the detector, which is specially developed for high resolution elastic recoil detection. Both the reconstructed spectrometer and the detector were adapted to the specific experimental conditions needed for high-resolution Ion beam analysis of light elements and tested for routine practice. The detector consists of two compo-nents. At the back end of the detector a Bragg ionization chamber is mounted, which is used for the particle identification. At the front end, directly behind the entrance window a proportional counter is mounted. This proportional counter includes a high-resistance anode. Thus, the position of the particles is determined in the detector. The following two points concern fundamental studies of ion-solid interaction. By using a magnetic spectrometer the charge state distribution of the particles scattered from the sample after a binary collision is both possible and necessary for the analysis. For this reason the charge states are measured and compared with existing models. In addition, a model is developed that takes into account the charge state dependent energy loss. It is shown that without the application of this model the depth profiles do not correspond with the quantitative measurements by conventional IBA methods and with the thickness obtained by transmission electron microscopy. The second fundamental ion-solid interaction is the damage and the modification of the sample that occurs during heavy ion irradiation. It is shown that the used energies occur both electronic sputtering and electronically induced interface mixing. Electronic sputtering is minimised by using optimised beam parameters. For most samples the effect is below the detection limit for a fluence sufficient for the analysis. However, the influence of interface mixing is so strong that it has to be included in the analysis of the layers of the depth profiles. It is concluded from these studies that at the Rossendorf 5 MV tandem accelerator chlorine ions with an energy of 20 MeV deliver the best results. In some cases, such as the analysis of boron, the energy must be reduced to 6.5 MeV in order to retain the electronic sputtering below the detection limit. The fourth focus is the study of the influence of specific sample properties, such as surface roughness, on the shape of a measured energy spectra and respectively on the analysed depth profile. It is shown that knowledge of the roughness of a sample at the surface and at the interfaces for the analysis is needed. In addition, the contribution parameters limiting the depth resolution are calculated and compared with the conventional ion beam analysis. Finally, a comparison is made between the high-resolution ion beam analysis and complementary methods published by other research groups. The fifth and last focus is the analysis of light elements in ultra thin layers. All models presented in this thesis to reduce the influence of beam damage are taken into account. The dynamic non-equilibrium charge state is also included for the quantification of elements. Depth profiling of multilayer systems is demonstrated for systems consisting of SiO2-Si3N4Ox-SiO2 on silicon, boron implantation profiles for ultra shallow junctions and ultra thin oxide layers, such as used as high-k materials

Dissertação de mestrado em Genética Molecular
Fabry disease (FD) is a lysosomal storage disorder caused by deficient or null production of the enzyme α-galactosidase A (α-Gal A) as a result of mutations in α-galactosidase A gene (GLA), located on the X chromosome. The systemic accumulation of α-Gal A substrates, which are excreted in urine, leads to progressive damage of several organs and tissues and ultimately results in death due to heart failure, renal failure and cerebrovascular accidents. Many studies are focused in diagnosing FD through measurement of α-Gal A activity in blood and of accumulated substrates, mainly globotriaosylceramide, in plasma or urine. Mass spectrometry techniques are extensively used for screening of FD and other lysosomal storage disorders. However, mass spectrometry is an expensive method, requires a specialized operator and involves complex equipment. Thin-layer chromatography, on the other hand, is a robust and well explored method suitable for analysis of a large number of samples. The collection of urine samples is easy and non-invasive, which facilitates the cooperation of the subjects, but urine samples are difficult to transport without degradation. In this study, the problematic of urine samples transport was overcome by using filter paper as a supporting material that allows shipping through general mail without deterioration. The high-performance thin-layer chromatography method conventionally used to analyse Gb3 in urine samples was successfully optimised to analyse urine in filter paper. Using this method 60% of the previously diagnosed FD patients revealed increased Gb3 levels and one patient on enzyme replacement therapy showed significant Gb3 reduction after three months of therapy. The developed screening method offers an easy and simple method for urine sample shipping without degradation and suitable for a mass screening and ERT follow up program.
A doença de Fabry (FD) é uma doença lisossomal de sobrecarga causada pela atividade deficiente da enzima α-galactosidase A (α-Gal A) do, como resultado de mutações no gene desta enzima (gene GLA), localizado no cromossoma X. A acumulação sistémica dos substratos da α-Gal A, que são excretados na urina, leva à lesão progressiva de vários órgãos e tecidos, conduzindo por fim à morte devido a falência cardíaca, falência renal e acidentes vasculares cerebrais. Vários estudos estão debruçados no diagnóstico da doença de Fabry através da medição da atividade da α-Gal A em sangue e de substratos acumulados, principalmente o globotriaosilceramida, em urina e plasma. As técnicas de espectrometria de massa são extensivamente no rastreio da doença de Fabry e outras doenças lisossomais de sobrecarga. Contudo, a espectrometria de massa é um método dispendioso, requer um operador especializado e envolve equipamentos complexos. A cromatografia em camada fina, por sua vez, é um método robusto e bem explorado adequado à análise de grandes grupos de amostras. A colheita de amostras de urina é fácil e não é invasiva, o que facilita a cooperação por parte dos dadores, mas as amostras de urina são difíceis de transportar sem que haja deterioração. Neste estudo, a problemática do transporte de amostras de urina foi ultrapassada utilizando o papel de filtro como material de suporte, permitindo que as amostras sejam enviadas por correio normal sem degradação. O método de cromatografia em camada fina de alta performance convencionalmente utilizado na análise de Gb3, em amostras de urina, foi otimizado com sucesso para analisar amostras de urina em papel de filtro. Recorrendo a esta metodologia, verificou-se que os níveis de Gb3 estavam aumentados em 60% dos doentes de Fabry previamente diagnosticados, e que um paciente em terapia enzimática de substituição mostrou uma redução significativa de Gb3 após três meses de terapia. O método de rastreio desenvolvido oferece um modo simples e fácil de envio das amostras de urina sem que haja degradação, sendo por isso, adequado para o rastreio em massa e seguimento dos pacientes em terapia.
Fundação para a Ciência e a Tecnologia (FCT) - Projeto PTDC/SAL‐BEB/100875/2008 “Fabry Screen – Screening for Fabry disease based on automatic classification of chromatographic images”

Migmatites are a common rock type in the Adirondack Mountains, NY. We analyzed a single sample of biotite-garnet-sillimanite paragneiss with foliation parallel leucosome along Route 22 south of Whitehall, NY in order to determine the timing of melting using both in-situ monazite and zircon U/Pb geochronology from the restite and leucosome layers of the same rock. Monazite was analyzed via in-situ EMPA on the Ultrachron microprobe at the University of Massachusetts. Zircon was analyzed via LA-ICP-MS (in-situ and mounted mineral separates) at the LaserChron Center. Monazite analyses from the restite yielded six compositionally distinct populations with dates of 1178 ± 16, 1139 ± 4, 1064 ± 6, 1049 ± 4, 1030 ± 5, and 1004 ± 10 Ma. Yttrium and heavy REEs decrease in monazite in two steps: one dramatic drop from ca. 1150 to 1065 Ma and another between ca. 1065 and 1050, interpreted to reflect two periods of garnet growth and melting. Analyses from the restite zircon separate yielded a significant single peak near 1050 Ma. These zircon grains exhibit fir-tree sector zoning texture which is interpreted to indicate crystallization from melt. Monazite from leucosome yielded a unimodal population at ca. 1050 Ma, however, backscatter images document alteration of monazite to apatite on the edges of the grains, and abundant uranothorite inclusions. Leucosome zircon analyses yielded a ca. 1150 Ma population from cores and a 1050 Ma population from rims. Cathodoluminescence imaging reveals that the zircon rims have textures indicative of fluid alteration. The data are consistent with these rocks undergoing two periods of melting. The first event at ca. 1150 Ma may have involved a non-garnet producing melting reaction, such as muscovite dehydration-melting. The second event at 1065 Ma involved significant garnet growth, interpreted to represent biotite dehydration-melting. Subsequently, the rocks underwent hydrothermal alteration at 1050 Ma. Monazite grains with dates at 1030 ± 5 and 1004 ± 10 Ma have higher yttrium concentrations suggesting garnet breakdown and monazite growth during decompression and retrograde metamorphism. A combination of monazite and zircon dating techniques from each compositional layer is necessary to constrain leucosome-restite relationships and to accurately interpret the timing of melting from migmatites that have experienced multiple phases of melting.

In the fight to reduce carbon emissions, it is easy to see the necessity of reducing energy consumption. Buildings consume a large amount of energy, and have significant potential for energy savings. One tool for realising these potential savings is building simulation. To be able to use building simulation, accurate models for windows are needed. The models include individual layer models, to determine the solar and longwave radiative behaviours, as well as whole-system models to determine heat flows through the various layers of fenestration systems. This thesis looks at both kinds of models for incorporating windows into building simulations. A new network whole-system model is implemented, and integrated into the California Simulation Engine building simulation software. This model is also used as the calculation engine for a stand-alone rating tool. Additionally, a measurement technique used to measure off-normal solar properties of drapery materials, as part of developing shading layer models, is investigated using a Monte Carlo simulation. The network model uses a very general resistance network, allowing heat transfer between any two layers in a complex fenestration system (CFS), whether they are adjacent or not, between any layer and the indoor or outdoor side, or between the indoor and outdoor sides, although this last case is unlikely. Convective and radiative heat transfer are treated using the same format, resulting in increased stability. This general resistance network is used to calculate indices of merit for the CFS using numerical experiments. This approach requires fewer iterations to solve than previous solution methods, and is more flexible. The off-normal measurement technique which was investigated used a sample holder inserted into an integrating sphere. This is a non-standard way of using an integrating sphere, and early analyses did not provide conclusive information as to the effect of the sample holder. A Monte Carlo analysis confirmed the amount of beam attenuation as being 20% for the sample holder used in the experiments. Also con firmed was the effectiveness of dual-beam integrating spheres in correcting for the presence of a sample holder. The stand-alone rating tool which uses the general network framework, incorporates an easy-to-use visual interface. This tool models multiple types of shading layers with no restrictions on how they are combined. Users can easily change any one layer to see the effects of different arrangements. Users may specify any combination of indoor and outdoor ambient and mean radiant temperatures, insolation, and beam/diffuse split.

碩士
國立中興大學
化學系所
107
A layered double hydroxide (LDH) material was prepared and coated onto the surface of glassy fiber as a sorbent of solid phase microextraction (SPME) to collect halo-phenols in aqueous samples by headspace sampling for GC-ECD analysis. The LDH material was prepared by mixing magnesium nitrate and aluminum nitrate in water homogeneously and adjusted the pH to 10, then reflux for 24 hrs at 100 oC. After washing with water to neutral and then by alcohol, the LDH was formed posterior to dry in an oven. The SPME-LDH sorbent was prepared by dip-coating a glassy fiber into a mixed solution of LDH and silicone adhesive several times and dried vertically. The effectiveness of LDH fiber preparation was identified their functional groups by FT-IR, and the surface was observed with SEM. A headspace sampling of halo-phenols from 10 mL aqueous sample in a 20 mL sampling-vial was examined. Factors affecting the sampling such as the pH and temperature of sample, stir-rate, salting-out effect, and extraction time were optimized. Results indicated that the sampling was optimal at pH 2.0, 30% NaCl addition, 1000 rpm stirring at 60 oC for 35 min. For desorption and analysis by GC-ECD, detections are linear in 0.05 - 7.5, 0.01 - 1.5, and 0.005 - 7.5 μgL-1 for trichlorophenol, tetrachlorophenol, tribromophenol and pentachlorophenol, respectively, with correlation coefficients (R2) in 0.9960 - 0.9978. Detection limits are in 1.3 - 14.6 ngL-1 and method detection limits are in 4.4 - 48.5 ngL-1. The method was used to analyze four halophenols in river water and in farm-soil samples, and no residuals of halophenols was found. When spiked standards in samples and analyzed by the method, the recoveries of halophenols were in 86.6 - 98.3% with RSD in 2.4 - 7.4 %, and in 86.6 - 98.5 % with RSD in 2.8 - 7.7 %, respectively. The prepared LDH absorbent for SPME sampling with advantages of easy preparation, thermal stability, low-costs, high-enrichment, no carry-over, and no organic solvent required. Thus, it is a simple, rapid, sensitive, inexpensive, and eco-friendly sample preparation method.

碩士
國立高雄大學
應用物理學系碩士班
99
This thesis studies the anisotropic properties of N-polar GaN, nonpolar a-plane GaN, and (11-22) semipolar InGaN/GaN MQW samples grown by MOVCD. The optical and material properties were investigated by photoluminescence (PL), and time-resolved PL measurements, atomic force microscopy (AFM), field-emission electron microscopy (FE-SEM), and cathodoluminescence (CL). First, for N-polar GaN samples, we study the effects of the buffer layer growth times on the material and optical properties of three N-polar GaN samples with different growth times (114, 120, and 180 seconds) of low temperature (LT) buffer layer. As the growth time of the low temperature buffer increases, the PL and CL intensities decrease, due to a rougher surface morphology. Also, the stress is associated with PL peak position by Raman scattering. Second, we study nonpolar a-plane GaN on r-sapphire with the different thickness first-step a-GaN. For nonpolar a-plane GaN samples, the main peak (~365 nm) in the CL spectrum is associated with the partial dislocation terminating basal stacking faults (BSFs) and two main peaks around ~355 nm and ~363 nm in PL the spectrum are attributed to near-band-edge (NBE) emission and BSFs, respectively. Third, for (11-22) semipolar InGaN/GaN MQW samples, the main peak around ~403 nm is the InGaN-related emission, while the other weak peaks are the GaN-related emission in the PL Spectrum. As the sample has the stronger CL luminescence, the striation feature with a rougher surface morphology can be observed.

In der vorliegenden Arbeit wird erstmals das QQDS-Magnetspektrometer für die höchstauflösende Ionenstrahlanalytik leichter Elemente am Helmholtz-Zentrum Dresden-Rossendorf umfassend vorgestellt. Zusätzlich werden sowohl alle auf die Analytik Einfluss nehmenden Parameter untersucht als auch Methoden und Modelle vorgestellt, wie deren Einfluss vermieden oder rechnerisch kompensiert werden kann. Die Schwerpunkte dieser Arbeit gliedern sich in fünf Bereiche. Der Erste ist der Aufbau und die Inbetriebnahme des QQDS-Magnetspektrometers, der zugehörige Streukammer mit allen Peripheriegeräten und des eigens für die höchstauflösende elastische Rückstoßanalyse entwickelten Detektors. Sowohl das umgebaute Spektrometer als auch der im Rahmen dieser Arbeit gebaute Detektor wurden speziell an experimentelle Bedingungen für die höchstauflösende Ionenstrahlanalytik leichter Elemente angepasst und erstmalig auf einen routinemäßigen Einsatz hin getestet. Der Detektor besteht aus zwei Komponenten. Zum einen befindet sich am hinteren Ende des Detektors eine Bragg-Ionisationskammer, die zur Teilchenidentifikation genutzt wird. Zum anderen dient ein Proportionalzähler, der eine Hochwiderstandsanode besitzt und direkt hinter dem Eintrittsfenster montiert ist, zur Teilchenpositionsbestimmung im Detektor. Die folgenden zwei Schwerpunkte beinhalten grundlegende Untersuchungen zur Ionen-Festkörper-Wechselwirkung. Durch die Verwendung eines Magnetspektrometers ist die Messung der Ladungszustandsverteilung der herausgestreuten Teilchen direkt nach einem binären Stoß sowohl möglich als auch für die Analyse notwendig. Aus diesem Grund werden zum einen die Ladungszustände gemessen und zum anderen mit existierenden Modellen verglichen. Außerdem wird ein eigens entwickeltes Modell vorgestellt und erstmals im Rahmen dieser Arbeit angewendet, welches den ladungszustandsabhängigen Energieverlust bei der Tiefenprofilierung berücksichtigt. Es wird gezeigt, dass ohne die Anwendung dieses Modells die Tiefenprofile nicht mit den quantitativen Messungen mittels konventioneller Ionenstrahlanalytikmethoden und mit der Dickenmessung mittels Transmissionselektronenmikroskopie übereinstimmen, und damit falsche Werte liefern würden. Der zweite für die Thematik wesentliche Aspekt der Ionen-Festkörper-Wechselwirkung, sind die Probenschäden und -modifikationen, die während einer Schwerionen-bestrahlung auftreten. Dabei wird gezeigt, dass bei den hier verwendeten Energien sowohl elektronisches Sputtern als auch elektronisch verursachtes Grenzflächendurchmischen eintreten. Das elektronische Sputtern kann durch geeignete Strahlparameter für die meisten Proben ausreichend minimiert werden. Dagegen ist der Einfluss der Grenzflächendurchmischung meist signifikant, so dass dieser analysiert und in der Auswertung berücksichtigt werden muss. Schlussfolgernd aus diesen Untersuchungen ergibt sich für die höchstauflösende Ionenstrahlanalytik leichter Elemente am Rossendorfer 5-MV Tandembeschleuniger, dass die geeignetsten Primärionen Chlor mit einer Energie von 20 MeV sind. In Einzelfällen, wie zum Beispiel der Analyse von Bor, muss die Energie jedoch auf 6,5 MeV reduziert werden, um das elektronische Sputtern bei der notwendigen Fluenz unterhalb der Nachweisgrenze zu halten. Der vierte Schwerpunkt ist die Untersuchung von sowohl qualitativen als auch quantitativen Einflüssen bestimmter Probeneigenschaften, wie beispielsweise Oberflächenrauheit, auf die Form des gemessenen Energiespektrums beziehungsweise auf das analysierte Tiefenprofil. Die Kenntnis der Rauheit einer Probe an der Oberfläche und an den Grenzflächen ist für die Analytik unabdingbar. Als Resultat der genannten Betrachtungen werden die Einflüsse von Probeneigenschaften und Ionen-Festkörper-Wechselwirkungen auf die Energie- beziehungsweise Tiefenauflösung des Gesamtsystems beschrieben, berechnet und mit der konventionellen Ionenstrahlanalytik verglichen. Die Möglichkeiten der höchstauflösenden Ionenstrahlanalytik werden zudem mit den von anderen Gruppen veröffentlichten Komplementärmethoden gegenübergestellt. Der fünfte und letzte Schwerpunkt ist die Analytik leichter Elemente in ultradünnen Schichten unter Berücksichtigung aller in dieser Arbeit vorgestellten Modelle, wie die Reduzierung des Einflusses von Strahlschäden oder die Quantifizierung der Elemente im dynamischen Ladungszustandsnichtgleichgewicht. Es wird die Tiefenprofilierung von Mehrschichtsystemen, bestehend aus SiO2-Si3N4Ox-SiO2 auf Silizium, von Ultra-Shallow-Junction Bor-Implantationsprofilen und von ultradünnen Oxidschichten, wie zum Beispiel High-k-Materialien, demonstriert.
In this thesis the QQDS magnetic spectrometer that is used for high resolution ion beam analysis (IBA) of light elements at the Helmholtz-Zentrum Dresden-Rossendorf is presented for the first time. In addition all parameters are investigated that influence the analysis. Methods and models are presented with which the effects can be minimised or calculated. There are five focal points of this thesis. The first point is the construction and commissioning of the QQDS magnetic spectrometer, the corresponding scattering chamber with all the peripherals and the detector, which is specially developed for high resolution elastic recoil detection. Both the reconstructed spectrometer and the detector were adapted to the specific experimental conditions needed for high-resolution Ion beam analysis of light elements and tested for routine practice. The detector consists of two compo-nents. At the back end of the detector a Bragg ionization chamber is mounted, which is used for the particle identification. At the front end, directly behind the entrance window a proportional counter is mounted. This proportional counter includes a high-resistance anode. Thus, the position of the particles is determined in the detector. The following two points concern fundamental studies of ion-solid interaction. By using a magnetic spectrometer the charge state distribution of the particles scattered from the sample after a binary collision is both possible and necessary for the analysis. For this reason the charge states are measured and compared with existing models. In addition, a model is developed that takes into account the charge state dependent energy loss. It is shown that without the application of this model the depth profiles do not correspond with the quantitative measurements by conventional IBA methods and with the thickness obtained by transmission electron microscopy. The second fundamental ion-solid interaction is the damage and the modification of the sample that occurs during heavy ion irradiation. It is shown that the used energies occur both electronic sputtering and electronically induced interface mixing. Electronic sputtering is minimised by using optimised beam parameters. For most samples the effect is below the detection limit for a fluence sufficient for the analysis. However, the influence of interface mixing is so strong that it has to be included in the analysis of the layers of the depth profiles. It is concluded from these studies that at the Rossendorf 5 MV tandem accelerator chlorine ions with an energy of 20 MeV deliver the best results. In some cases, such as the analysis of boron, the energy must be reduced to 6.5 MeV in order to retain the electronic sputtering below the detection limit. The fourth focus is the study of the influence of specific sample properties, such as surface roughness, on the shape of a measured energy spectra and respectively on the analysed depth profile. It is shown that knowledge of the roughness of a sample at the surface and at the interfaces for the analysis is needed. In addition, the contribution parameters limiting the depth resolution are calculated and compared with the conventional ion beam analysis. Finally, a comparison is made between the high-resolution ion beam analysis and complementary methods published by other research groups. The fifth and last focus is the analysis of light elements in ultra thin layers. All models presented in this thesis to reduce the influence of beam damage are taken into account. The dynamic non-equilibrium charge state is also included for the quantification of elements. Depth profiling of multilayer systems is demonstrated for systems consisting of SiO2-Si3N4Ox-SiO2 on silicon, boron implantation profiles for ultra shallow junctions and ultra thin oxide layers, such as used as high-k materials.