The marginal glass-forming alloys have attracted much attention due to unique products of devitrification with a very high number density of nuclei up to 10^23 m^-3. Among these alloy systems, utmost interest is given to Al-RE and Al-TM-RE alloys with excellent lightweight mechanical (fracture strength close to 1 GPa) and chemical properties attributed to the presence of an extremely high density of nanocrystals embedded in an amorphous matrix. Classical nucleation theory fails in explaining this abnormal nucleation behavior, several other mechanisms have been proposed / however, there is still no agreement on the exact nucleation mechanism. Al-Tb system was investigated in liquid and solid amorphous states with a collective study of ab-initio MD and RMC simulations and state of art X-rays and e-beam techniques. Regions of pure Al clusters in the solid and liquid states were detected with the sizes extending up to 1-2 nm length. Al clusters interconnecting regions lead to formation of RE rich MRO structure which gave rise to the pre-peak in S(Q)-Q data in liquid and solid states. Specimens having MRO were crystallized within a controlled atmosphere and temperature and investigated using a combined study of TEM, HRTEM, SEM, XRD and DSC. HRTEM investigations and JMA results indicated different mechanism of nucleation. Therefore the kinetics of highly populated nuclei formation was found too complicated to be explained by well-known JMA approach. Mechanical tests were applied to determine the effects of morphology and populations of nanocrystals embedded in amorphous matrix. The tensile tests and the subsequent fracture surface analysis indicated brittle type of failure and the formation of shear bands, respectively. Relatively high hardness and tensile strength were detected by nanocrystallization.

Biological tissues were studied with synchrotron infrared (IR) microspectroscopy, a technique that allows the spatially resolved determination and mapping of multiple components in situ at high spatial resolution. The first project involved studying brain tissue from TgCRND8 mice, a transgenic model of Alzheimer’s disease (AD). AD is the main cause of dementia in the ageing population, marked by the deposition of plaques composed of the Aβ peptide. Dense-cored and diffuse plaques were IR mapped and the results correlated with histochemistry and immunostaining. Spectral analysis confirmed that congophilic plaque cores were composed of highly aggregated protein in a β-sheet conformation. The amide I maximum of plaque cores was 1623 cm-1; there was no evidence of the high frequency (1680-1690 cm-1) peak seen in in vitro Aβ fibrils and attributed to anti-parallel β-sheet. A significant elevation in phospholipids was found around dense-cored plaques in TgCRND8 mice ranging in age from 5 to 21 months. This was due to an increase in cellular membranes from dystrophic neurites and glial cells around the core, but could also contribute to Aβ aggregation through the interaction of newly secreted Aβ with phospholipids. In contrast, diffuse plaques were not associated with infrared detectable changes in protein secondary structure or relative concentrations of other tissue components. In addition, focally elevated deposits of creatine, a molecule with a crucial role in energy metabolism, were discovered in AD brain tissue with IR microspectroscopy. The creatine deposits may be a previously undiscovered disease marker. A second project was part of a larger Natural Sciences and Engineering Research Council Collaborative Health Research Project (NSERC-CHRP) to test the hypothesis that treatment with anti-oxidants, L-2-oxo-thiazolidine-4-carboxylate (OTC) and quercetin, following spinal surgery may reduce oxidative stress, inflammation, and scarring. The effect of OTC and quercetin on scar tissue formation was evaluated in rats that had undergone laminectomy. Synchrotron IR microspectroscopy data were collected on scar tissue from OTC, quercetin and saline (control) treated animals, sacrificed at 3 and 21 days post-surgery. Spectral differences could be correlated with the stages of wound healing. / May 2007

Compounds forming alloys with lithium, such as silicon or tin, are promising negative electrode materials for the next generation of Li-ion batteries due to their higher theoretical capacity compared to the current commercial electrode materials. An important issue is to better understand the phenomena occurring at the electrode/electrolyte interfaces of these new materials. The stability of the passivation layer (SEI) is crucial for good battery performance and its nature, formation and evolution have to be investigated. It is important to follow upon cycling alloying/dealloying processes, the evolution of surface oxides with battery cycling and the change in surface chemistry when storing electrodes in the electrolyte. The aim of this thesis is to improve the knowledge of these surface reactions through a non-destructive depth-resolved PES (Photoelectron spectroscopy) analysis of the surface of new negative electrodes. A unique combination utilizing hard and soft-ray photoelectron spectroscopy allows by variation of the photon energy an analysis from the extreme surface (soft X-ray) to the bulk (hard X-ray) of the particles. This experimental approach was used to access the interfacial phase transitions at the surface of silicon or tin particles as well as the composition and thickness/covering of the SEI. Interfacial mechanisms occurring upon the first electrochemical cycle of Si-based electrodes cycled with the classical salt LiPF6 were investigated. The mechanisms of Li insertion (LixSi formation) have been illustrated as well as the formation of a new irreversible compound, Li4SiO4, at the outermost surface of the particles. Upon long cycling, the formation of SiOxFy was shown at the extreme surface of the particles by reaction of SiO2 with HF contributing to battery capacity fading. The LiFSI salt, more stable than LiPF6, improved the electrochemical performances. This behaviour is correlated to the absence of SiOxFy upon long-term cycling. Some degradation of LiFSI was shown by PES and supported by calculations. Finally, interfacial reactions occurring upon the first cycle of an intermetallic compound MnSn2 were studied. Compared to Si based electrodes, the SEI chemical composition is similar but the alloying process and the role played by the surface metal oxide are different.

A written report of a paper titled Holographic dual of collimated radiation by Veronika E. Hubeny where a new and easier method is proposed to estimate the “radiation due to an accelerated quark in a strongly coupled medium”. The method is able to reproduce the results from an earlier paper without the need of solving the linearized Einstein equations but by way of calculating geodesics in AdS using the AdS/CFT correspondence and the gravitational dual of the quark being a string. A quick introduction to synchrotron radiation and general relativity is given after which the AdS/CFT correspondence is introduced along with the results and method of V. Hubeny. / A bachelor thesis in theoretical physics.

Chromium (VI) is a pervasive groundwater contaminant that poses a considerable threat to human health. Remediation techniques have focused on the reduction of the highly mobile Cr(VI) to the sparingly soluble, and less toxic, Cr(III) species. Traditionally, remediation performance has been evaluated through the measurement of Cr(VI) concentrations; however, this method is both costly and time-consuming, and provides little information regarding the mechanism of Cr(VI) removal. More recently, Cr isotope analysis has been proposed as a tool for tracking Cr(VI) migration in groundwater. Redox processes have been shown to produce significant Cr isotope fractionation, where enrichment in the ⁵³Cr/⁵²Cr ratio in the remaining Cr(VI) pool is indicative of a mass-transfer process. This thesis describes laboratory batch and column experiments that evaluate the Cr isotope fractionation associated with the reduction of Cr(VI) by various materials and under various conditions. Laboratory batch experiments were conducted to characterize the isotope fractionation during Cr(VI) reduction by granular zero-valent iron (ZVI) and organic carbon (OC). A decrease in Cr(VI) concentrations was accompanied by an increase in δ⁵³Cr values for the ZVI experiments. Data were fitted to a Rayleigh-type curve, which produced a fractionation factor α = 0.9994, suggesting a sorption-dominated removal mechanism. Scanning electron microscopy (SEM), X-ray absorption near-edge structure (XANES) spectroscopy, and X-ray photoelectron spectroscopy (XPS) indicated the presence of Cr(III) on the solid material, suggesting that reduction of Cr(VI) occurred. A series of batch experiments determined that reaction rate, experimental design, and pre-treatment of the ZVI had little to no effect on the Cr isotope fractionation. The interpretation of isotope results for the organic carbon experiments was complicated by the presence of both Cr(VI) and Cr(III) co-existing in solution, suggesting that further testing is required. A laboratory column experiment was conducted to evaluate isotopic fractionation of Cr during Cr(VI) reduction by OC under saturated flow conditions. Although decreasing dissolved Cr(VI) concentrations also were accompanied by an increase in δ⁵³Cr values, the isotope ratio values did not fit a Rayleigh-type fractionation curve. Instead, the data followed a linear regression equation yielding α = 0.9979. Solid-phase analysis indicated the presence of Cr(III) on the surface of the OC. Both the results of the solid-phase Cr and isotope analyses suggest a combination of Cr(VI) reduction mechanisms, including reduction in solution, and sorption prior to reduction. The linear characteristic of the δ⁵³Cr data may reflect the contribution of transport on Cr isotope fractionation.

Analysis of the electronic structures of nitrogen-doped, amorphous carbon samples and of nanodiamond films are carried out in order to determine their sp2 bonding concentration. The amorphous carbon samples under consideration are deposited onto polytetrafluoroethylene (PTFE) polymer substrates by hot wire plasma sputtering of graphite in varying nitrogen concentration atmospheres. The deposition or modification of the substrates surface may lend itself to increasing hardness and wear resistance. Eventually these polymer substrates may be used for applications in the field of biomaterials, focusing on cardiovascular surgery, where a low blood/surface interaction is important. The primary technique used in this study is x-ray absorption spectroscopy, measured at the Advanced Light Source synchrotron at the Lawrence Berkeley National Laboratory, Berkeley, USA. A method of analyzing these spectra was then developed to determine the sp2 bonding concentrations in carbon films. Through this newly developed analysis method, the sp2 bonding concentrations in these samples increases from 74 to 93% with growing nitrogen doping. The diamond films presented here are deposited on silicon wafer substrates in a methane atmosphere by microwave plasma deposition. Various deposition conditions, such as bias voltage and methane atmosphere concentration, affect the purity of the diamond film. This analysis reveals sp2 bonding concentrations in these samples from, typically, a few percent to 25%.

<p>Silicon ceramics are popular in both commercial applications and material research. The purpose of this thesis is to present measurements and analysis of four different silicon ceramics: á, â and ã phases of silicon nitride and silicon oxynitride using soft x-ray spectroscopy, which analyses the electronic structure of materials by measuring the absorption and emission of x-ray radiation. Absorption and emission spectra of these materials are presented, many of which have not be previously documented. The results are compared to model spectra and together they provide information about the electronic structure of the material.</p><p>Assignments of emission features to element, orbital, and site symmetry are performed for each material. Combinations of silicon and nitrogen emission spectra provide insight into the strained bonding structure of nitrogen. It is concluded that p-dð interaction plays a role in the bonding arrangement of nitrogen and oxygen sites within these structures. The emission features of non-equivalent silicon sites within ã-Si3N4 are identified, which represents some of the first analysis of same element, non-equivalent sites in a material.</p><p>Silicon absorption and emission spectra were plotted on the same energy scale to facilitate measurement of the band gap. Since previously measured band gaps are not well represented in literature, the measured band gaps were compared to values predicted using DFT calculations. The band gap values are in reasonable agreement to calculated values, but do not vary as widely as predicted.</p>

The optical design of a soft X-ray (90-1100~eV) emission spectrometer for the Resonant Elastic and Inelastic X-ray Scattering (REIXS) beamline to be implemented at the CLS is presented. An overview of soft X-ray optical theory as it relates to diffraction gratings is given. The initial constraints and the process that led to this design are outlined. Techniques and software tools that were developed, using ray-tracing and diffraction grating efficiency calculations, are discussed. The analysis completed with these tools to compare existing soft X-ray emission spectrometer designs is presented. Based on this analysis, a new design with superior performance for this application is proposed and reviewed. This design employs Rowland circle geometry to achieve a resolving power in excess of 2,500 in the range of interest. In addition, a novel design is proposed for a larger extremely high resolution spectrometer which will provide resolving powers exceeding 10,000 throughout the higher end of this range. A review is given of research into the components, manufacturing techniques and tolerances that will be required to produce this spectrometer.

Positioning, immobilization, and organ motion are some of the major concerns in all imaging modalities. With synchrotron X-ray imaging, alignment of the region of interest to the beam is usually done inside the experimental hutch. However, because specimen alignment can be time consuming; such a system is wasteful of valuable beam time. For the purposes of the Biomedical Imaging and Therapy (BMIT) beamlines at the Canadian Light Source, we propose an effective and versatile means of positioning a wide range of subjects (human and animal) with a wide range of sizes using a laser-based fiducial system to define the region of interest (ROI) before imaging; i.e., outside the experimental hutch. This system will allow the beam path through a specific region of interest to be modeled outside the imaging hutch in a way that it can be reproduced relative to the fixed X-ray beamline inside the hutch. The model will include an indication of the center of the beam and a rectangular area around the target delineating the limits of the area to be imaged (i.e., encompassing the region of interest). The rectangular field of view would be projected on the incoming (entrance) side of the subject as well as the outgoing (exit) side of the subject, and these projections must be coaxial with each other and parallel with the X-ray beam. This method is user friendly, allows mistake to be corrected before experiment and most importantly saves time.

The development of a non-invasive method of visualizing gene expression in larger animals could revolutionize some aspects of gene research by opening up a wider variety of animal systems to explore; some of which may be better models of human systems. Presently, most gene expression studies employ Green Fluorescent Protein (GFP) transfected into the genome of the animal system. For larger animals, an x-ray equivalent of GFP would be desirable due to the high penetrating power of x-rays. A model gene modification system is to use the Sodium (Na) Iodide Symporter (NIS) which will cause the accumulation of iodine in cells which express the NIS. To non-invasively observe the dilute iodine accumulated by the cancer cells transfected with NIS in the head of small animals, such as a rat, two synchrotron-based imaging methods were studied: K-Edge Subtraction (KES) imaging and Fluorescence Subtraction Imaging (FSI).<p> KES needs wide monochromatic x-ray beams at two energies bracketing the K-edge of the contrast agent existing or injected in the tissues. The monochromatic beam in the synchrotron facility normally is prepared by a double crystal monochromator. The appearance of the azimuthal angle (tilt error) in the double crystal monochromator creates intensity variations across the imaging field. This misalignment was studied through another two synchrotron-based imaging methods, Diffraction Enhanced Imaging (DEI) and Multi-Image Radiography (MIR), which show this problem clearly in their processed images. The detailed analysis of the effect of the tilt error, how it affects the resulting images, and how to quantify such an error were presented in the thesis. A post processing method was implemented and the artifacts caused by the improper experimental settings were discussed.<p> With the wide monochromatic beam prepared by the double crystal monochromator, a sequence of KES experiments were done and the detection limit of KES was quantified at a projected amount of 17.5mM-cm iodine in a physical model of a rat head with a radiation dose of 2.65mGy. With the raster scan of the object relative to the monochromatic pencil beam, FSI was studied to obtain higher Signal to Noise Ratio (SNR) for local area and better detection limit compared to KES. The detection limit of FSI was measured as a projected amount of 2.5mM-cm iodine in the same physical rat head with a tolerable radiation dose of 24mGy. According to the comparison of these two imaging techniques with references to imaging time and area, radiation dose, spatial resolution, and SNR, it was concluded that these two imaging techniques can be used complementarily in imaging dilute contrast material. Due to the short imaging time and large imaging area, KES is used first to provide a global view of the object, locate the area of interest, do the preliminary diagnosis, and decide whether the further FSI is necessary. Due to its high SNR for the dilute sample, FSI can be used when the area of interest is known. The combination of these two imaging techniques will be very promising and powerful. To facilitate the comparison of KES and FSI, a quality factor was developed to evaluate the performance of the imaging system.<p> The measured detection limits in our experiments are far beyond the thyroidal iodine concentration of a rat (around 1mM). To further improve the performance of KES, a bent Laue crystal monochromator was designed to do the simultaneous iodine KES imaging which overcomes the artifacts in the iodine image caused by the temporal difference for a single set of images. The designed monochromator can provide two separated x-ray beams bracketing the K-edge of iodine at the same time with a very high spatial resolution which is only depends on the source size, a very high energy resolution which can almost compete with that of the double crystal monochromator, and an acceptable photon flux.