Thesis (Ph. D.)--University of Washington, 1997. / Vita. Includes bibliographical references (leaves [161]-163).

Thesis (M.S.)--West Virginia University, 2008. / Title from document title page. Document formatted into pages; contains xi, 108 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 85-93).

Thesis (Ph. D.)--West Virginia University, 2005. / Title from document title page. Document formatted into pages; contains xi, 99 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 93-99).

Made available in DSpace on 2014-10-09T12:52:01Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:53Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

abstract: The structure-function relation in Biology suggests that every biological molecule has evolved its structure to carry out a specific function. However, for many of these processes (such as those with catalytic activity) the structure of the biomolecule changes during the course of a reaction. Understanding the structure-function relation thus becomes a question of understanding biomolecular dynamics that span a variety of timescales (from electronic rearrangements in the femtoseconds to side-chain alteration in the microseconds and more). This dissertation deals with the study of biomolecular dynamics in the ultrafast timescales (fs-ns) using electron and X-ray probes in both time and frequency domains. It starts with establishing the limitations of traditional electron diffraction coupled with molecular replacement to study biomolecular structure and proceeds to suggest a pulsed electron source Hollow-Cone Transmission Electron Microscope as an alternative scheme to pursue ultrafast biomolecular imaging. In frequency domain, the use of Electron Energy Loss Spectroscopy as a tool to access ultrafast nuclear dynamics in the steady state, is detailed with the new monochromated NiON UltraSTEM and examples demonstrating this instrument’s capability are provided. Ultrafast X-ray spectroscopy as a tool to elucidate biomolecular dynamics is presented in studying X-ray as a probe, with the study of the photolysis of Methylcobalamin using time-resolved laser pump – X-ray probe absorption spectroscopy. The analysis in comparison to prior literature as well as DFT based XAS simulations offer good agreement and understanding to the steady state spectra but are so far inadequate in explaining the time-resolved data. However, the trends in the absorption simulations for the transient intermediates show a strong anisotropic dependence on the axial ligation, which would define the direction for future studies on this material to achieve a solution. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

Made available in DSpace on 2014-10-09T12:52:01Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:53Z (GMT). No. of bitstreams: 0 / A difração de raios X e de elétrons retroespalhados, em escalas distintas, foram aplicadas para acompanhar mudanças microestruturais em dois aços ferríticos baixo carbono (2%Si e ABNT 1006), observando-se o desenvolvimento da textura nas etapas de laminação a frio (skin-pass) e recozimento a 760 oC. Para ambos os aços, os resultados permitiram afirmar que o fenômeno que ocorre após a laminação por skin-pass e tratamento térmico, nas condições deste trabalho, é a recristalização primária. A aplicação do skin-pass criou mais discordâncias em grãos com baixo fator de Taylor por sofrerem mais deformações. Observou-se a nucleação e crescimento de grãos em regiões de grande densidade de células de discordâncias. A presença do silício atrasou a recuperação favorecendo o aumento de subcontornos. Não foi observado o crescimento anormal de grãos, nem em função da presença de grãos Goss. Os contornos CSL não garantiram o crescimento do grão. Núcleos de crescimento de grãos deram origem a grãos com orientações distintas, indicando que o crescimento de grãos não dependeu da existência prévia de grãos com as orientações desenvolvidas, demonstrando que o crescimento anormal de grãos não está relacionado necessariamente com os grãos Goss. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Electron crystallography is complementary to X-ray crystallography. Single crystal X-ray diffraction requires the size of a crystal to be larger than about 5 × 5 × 5 μm3 while a TEM allows a million times smaller crystals being studied. This advantage of electron crystallography has been used to solve new structures of small crystals. One method which has been used to collect electron diffraction data is rotation electron diffraction (RED) developed at Stockholm University. The RED method combines the goniometer tilt and beam tilt in a TEM to achieve 3D electron diffraction data. Using a high angle tilt sample holder, RED data can be collected to cover a tilt range of up to 140o.  Here the crystal structures of several different compounds have been determined using RED. The structure of needle-like crystals on the surface of NiMH particles was solved as La(OH)2. A structure model of metal-organic layers has been built based on RED data. A 3D MOF structure was solved from RED data. Two halide perovskite structures and two newly synthesized aluminophosphate structures were solved. For those beam sensitive crystals characterized here, sample cooling down to -170oC was used to reduce the beam damage. The low temperature not only reduces electron beam damage, but also keeps the structure more stable in the high vacuum in a TEM and improves the quality of the diffraction data. It is shown that cooling can improve the resolution of diffraction data for MOFs and zeolites, for samples undergoing phase changes at low temperature, the data quality could be worse by cooling. In summary, cooling can improve the ED data quality as long as the low temperature does not trigger structural changes. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Manuscript. Paper 3: Submitted.</p>

In this thesis three studies of the geometric structure of the (110) surface of single crystal rutile TiO2 are presented. Firstly, quantitative low energy electron diffraction (LEED-IV) data acquired from TiO2(110)(1x1) are reanalysed to confirm the integrity of the previously reported optimized geometries by performing structural optimisation as a function of depth into the selvedge. The second study addresses the geometry of the x-linked (1x2) reconstruction of the same surface. Again, LEED-IV data are analysed to quantitatively determine the surface structure. Part of this effort involved substantial development of the code (SATLEED) employed for simulating the experimental data, to allow simultaneous optimisation of more than one surface termination. In contrast to recent scanning probe work, the analysis indicates that the surface consists of two differently relaxed Ti2O3 added rows. The last study concerns ab initio calculations of the structure of benzoate on TiO2(110)(1x1). Of particular interest is the impact of surface coverage on the orientation of the benzene ring. It is predicted that the benzene ring twists and tilts away from high symmetry with increasing coverage due to adsorbate-adsorbate interactions. No evidence is found to support the formation of benzoate dimers or trimers, as was concluded in earlier experimental work.

This experimental work aims to characterize the SiC layer of various Tri-Structural Isotropic (TRISO) coated fuel particles. In the first part of the work, Raman spectroscopy is used to qualitatively characterize the SiC TRISO layer and to identify the presence of silicon from peak positions. Free silicon poses a significant threat to the integrity of the SiC layer because it melts at 1414oC, significantly lower than the maximum operating temperature of 1550oC. Crystalline silicon is characterized with qualitative Raman spectroscopy by a 520 cm-1 peak. Silicon is found to be preferentially concentrated along the SiC layer close to the inner pyrolytic carbon (IPyC) layer. Samples that were only mounted and polished are compared with those that have in addition also been etched. Disordering of the crystals and peak splitting necessitated the use of peak de-convolution. The 3C, 6H and 15R polytypes of SiC were identified. The second part of the Raman spectroscopy work involves the development of calibration curves using peak areas from known binary mixtures (5%, 25%, 50% and 75% Si) to quantify the amount of silicon found relative to SiC. Initially the SiC polytypes used in these mixtures are 3C, 4H and 6H. Reasonably good logarithmic calibration fits were obtained with R2 values of 0.996, 0.966 and 0.988 respectively. However some error accompanied the calibration values and an average of ten analyses yielded a more reliable average. The calibration curve results made it possible to estimate the silicon content throughout the SiC layer for each sample, when combining the results of the qualitative and quantitative Raman spectroscopic study. Samples PO6 and PO8 revealed high peaks of crystalline silicon. When peak areas were quantified and related to the 3C calibration curve, as much as 60% silicon was calculated for both samples. Etching was found to slightly lower the silicon to SiC ratio. The calibration accuracy for the binary mixtures was checked by plotting calculated values against weighed-off values, yielding 3C, 4H and 6H straight-line fits with R2 values of 0.983, 0.941 and 0.981 respectively. These binary mixtures were analyzed with the SEM, which revealed variable particle size and segregation of silicon and SiC. Quantitative Raman spectroscopy is however known to be affected by a significant number of variables that are difficult to control. Attempts were made to decrease the scatter of the results from the calibration curve to yield more precise results. Two pure samples of silicon and SiC were studied separately, in attempts to better understand particle size and distortion effects. Distortion was found to have a greater impact on the scatter of peak area values than particle size. The scatter associated with pure sample peak areas casts doubt on the accuracy of the binary calibration curves. Rietveld analysis using X-ray powder diffraction is used to further support the Raman spectroscopy work by qualitatively and quantitatively characterizing the phases involved in each TRISO particle, to a greater degree of accuracy than the Raman spectroscopy. Refinement components include 2H graphite, quartz, SiC (3C, 6H, 8H and 15R), silicon and tetragonal ZrO2. Oxidized samples were compared with unoxidized samples. The outer pyrolytic carbon (OPyC) layer was oxidized (to improve the accuracy of quantitative measurements). Graphite percentages dominated the refinements with values ranging from 57% to 90% for unoxidized samples and 28% to 83% for oxidized samples. The 3C SiC polytype is the most abundant polytype and constitutes 78% to 83% of the SiC (unoxidized samples) and 82% to 90% (oxidized samples). Trace percentages of silicon were detected for PO6 (0.4%), PO8 (0.6%) and PO10 (0.1%) Quantitative XRD results are known to be accurate to around 1% at the 3ó level. Calibration curves were also subsequently constructed from the same samples as those used for quantitative Raman spectroscopy by comparing the weighed-off values to the measured ones. The 3C, 4H and 6H R2-fits are 0.991, 0.978 and 0.984 respectively. All the milled samples contained significant α-Fe which contaminated the samples from the grinding process. After dissolving the α-Fe in HCl a sample was tested to check the effect of the α-Fe specifically on microabsorption. Microabsorption was found to be an insignificant effect. The second part of the XRD work focused on the high-temperature stability of SiC up to 1400oC. Al2O3 was used as the standard and the instrument was calibrated using its two independent lattice parameter values along the a-axis and c-axis to make temperature corrections. Temperature corrected curves (of SiC and graphite) were constructed, which superimposed the theoretical Al2O3 curve along the a-axis and c-axis. The linear thermal expansion coefficients of SiC and graphite could then be determined from corrected lattice parameter values. The thermal expansion coefficients of G102 SiC had similar values to the literature values up to 800oC. Thereafter the experimental values had significantly higher thermal expansivity when compared to literature values. PO4 and PO9 thermal expansion coefficient values were higher below 500oC, but much closer as temperatures approached 1400oC. There was little correlation between G102, PO4 and PO9 graphite c-axis thermal expansion coefficient curves and literature values. The third section of the work involves the characterization of the SiC layers of three of the samples by transmission electron microscopy using their selected area electron diffraction patterns. This facilitates the unequivocal characterization of the SiC polytypes. The 3C and 6H polytypes were identified. There is substantial disorder in the crystals. Planar defects of differing periodicity are seen along the [111] direction of the 3C polytype. Copyright / Dissertation (MEng)--University of Pretoria, 2010. / Materials Science and Metallurgical Engineering / unrestricted

abstract: X-ray free electron lasers (XFELs) provide several orders of magnitude brighter x-rays than 3rd generation sources. However, the electron beamlines and undulator magnets required are on the scale of kilometers, costing billions of dollars with only a half dozen or so currently operating worldwide. One way to overcome these limitations is to prebunch the electron beam on the scale of the x-ray wavelength. In this paper one such scheme is discussed, which uses a nanopatterned grating called a dynamical beam stop. This uses diffraction from crystal planes of the etched portion of a grating to impart a transverse modulation which becomes a temporal modulation via an emittance exchange (EEX). To expand upon this topic, dynamical electron diffraction intensities for a 200 nm thick Si(001) unpatterned membrane are simulated via the multislice method and compared to experiment for various crystallographic orientations at MeV energies. From this as well as an analysis of the experimental inelastic plasmon diffuse scattering, it is determined that the optimal transverse modulation would be formed from a bright field image of the beam stop, with the nanopattern being etched all the way through the membrane. A model quantifying the quality of the modulation - the bunching factor - as a function of contrast and duty factor is formulated and the optimal modulation is determined analytically. A prototype beam stop is then imaged in a transmission electron microscope (TEM) at 200 KeV, with the measured bunching factor of 0.5 agreeing with the model and approaching a saturated XFEL. Using the angular spectrum method, it is determined that the spatial coherence of the MeV energy electron beam is insufficient for significant self-imaging to occur for gratings with pitches of hundreds of nanometers. Finally, the first-order EEX input requirements for the electron beam are examined in the transverse dimension as are newly proposed longitudinal requirements to compensate for lingering correlations between the initial and final longitudinal phase spaces. / Dissertation/Thesis / Doctoral Dissertation Physics 2020