Graphene, the first two-dimensional crystal ever found, is a material that has attracted fervent and sustained interest from condensed matter researchers from around the world. It has a unique and unprecedented band structure in a bulk material: the bands near the Fermi level are linear, leading to massless charge carriers that propagate at the speed of light. However, graphene does not possess a band gap, and as such, it cannot be used to process information in any electronic device that uses digital logic. Graphene is oxidized when several different basic functional groups like hydroxyls, carboxyls, and epoxides bond to the hexagonal carbon basal plane to make graphene oxide (GO). The result is a nonstoichiometric and highly disordered system that, according to the results shown in this thesis, consists of zones of densely-packed functional groups interspersed between zones of relatively small functional group concentration. This has been confirmed by DFT calculations presented here, which is the first time that a successful simulation of the GO density of states has been compared to X-ray data. Contrary to many assumptions in the literature, many of the features in the density of states of GO are due not to carbon sites bonded to functional groups, but are due to nearby non-functionalized carbon sites. The band gap of graphene oxide is principally controlled by oxidation level. Reduction, followed by heating, will regenerate the near-Fermi states and close the band gap significantly as has been seen by others. However, heating non-reduced graphene oxide can also result in a much-reduced band gap, which occurs because intercalated water can react with the heated GO sample to remove functional groups by creation and eventual expulsion of carbon dioxide. The band gap of GO is further complicated by stacking effects if it is multilayered, because residual pi-conjugated states in neighboring planes interact. The two major types of stacking in graphite are AA-stacking and AB-stacking. AA-stacking interactions cause the pi * resonance to broaden and push states to lower energy, which means that AA-stacking determines the width of the gap in highly oxidized samples. However, direct oxidation of graphene is not the only way that one alter the electronic structure of GO. Other results presented here also show that non-covalent functionalization of graphene oxide by amorphous solid water is a powerful, reversible way to dramatically change the GO electronic structure.

X-ray absorption is not only element specific, but atom specific: two atoms of the same element in different states or in different neighbourhoods will have slightly different absorption characteristics. These energy dependent atomic form factors are carried over to the diffraction intensities. The atomic form factors are sensitive not only to the the energy of the X-ray but also the diffraction criteria; providing individual local physical data at different ratios in various diffractions. This process is referred to as site selectivity, it is unique to Diffraction Spectroscopy, and is achieved only when the sample is in crystal form. Through this work, a technique has been devised to site-separate two atoms of iron from within a protein, that builds on prior small unit cell Diffraction Anomalous Fine Structure experiments and harnesses the collection and processing software commonly used in large unit cell crystallography. A technique (dev + PCA) has been developed to retrieve the small signals from individual atom-labels out of the large and noisy background of real diffraction taken across a spectrum. The intensity of the diffractions are calculated by integrating over multiple images, profiling spots, merging datasets, and scaling across the whole spectrum. This thesis explores how Diffraction Spectroscopy can be used effectively on large unit cells, namely those of proteins. Site-selective absorption experiments were conducted on large unit cell crystals at a 3rd generation beamline, exclusively using existing equipment. The spectra generated were limited in scope but are an adequate proof of concept.

Porous, high surface area activated carbon (AC) can be used to remove certain irritating and toxic gases from contaminated air streams. Impregnating AC with carefully selected chemicals can improve ACs adsorption capacity for certain gases and provide adsorption capacity for gases that un-impregnated AC cannot fi lter. Impregnated activated carbons (IACs) and ACs can be used as the active component in respirators. Comparative studies of di fferent commercially available AC samples and of IAC samples, prepared from a wide variety of di fferent chemicals, were performed. The gas adsorption capacity of the samples was tested using sulfur dioxide (SO2), ammonia (NH3), hydrogen cyanide (HCN) and cyclohexane (C6H12) challenge gases and compared to results obtained from a commercially available broad spectrum respirator carbon. The samples were characterized using wide angle x-ray di raction (XRD), small angle x-ray scattering (SAXS), nitrogen adsorption isotherms, thermal gravimetric analysis (TGA) and scanning electron microscopy (SEM). Highlights of this work include the discovery of a IAC sample prepared from zinc nitrate (Zn(NO3)2) and nitric acid (HNO3) that, after heating at 180 C under argon, had overall dry gas adsorption capacity that was greater than the commercially available sample. The importance of pore size on the C6H12 adsorption capacity of AC was demonstrated using SAXS and nitrogen adsorption data. A relationship between decreased humid C6H12 capacity and pre-adsorbed water was shown using SAXS, TGA and gravimetric studies.

Pulsar wind nebulae (PWNe), nebulae harbouring a rotation-powered neutron star that was born in a supernova, provide opportunities to study highly relativistic pulsar winds and their interaction with the surrounding medium. Particularly interesting are PWNe that do not show any sign of the expected surrounding SNR shell and were thought to be born in subenergetic explosions or with unusual progenitors. The detection of a shell around one such PWN suggested that shells are indeed produced but may be faint due to unseen shocked ejecta, a low density environment, and/or a young age that has not yet allowed the shell to brighten and become visible. Here, by using observational X-ray data from modern telescopes with excellent spatial and energy resolution (Chandra and XMM-Newton), we target PWNe that do not have prominent SNR shells, and are known to be in varied environments, to further explore the characteristics of this growing, but poorly explored, class of PWNe. By combining imaging and spectroscopic results, we study the morphology of the PWNe, search for thermal emission from shock-heated material, investigate the energetics of the nebulae, and search for candidates for the neutron stars powering the nebulae. We find that while the faint shell surrounding G21.5–0.9 can be explained as a young PWN evolving in a low density medium, CTB 87 (G74.9+1.2) appears to be in an advanced stage of evolution, and G63.7+1.1 appears to be both in an advanced stage of evolution and in a dense environment. By performing spatially resolved spectroscopy, we have shown how the spectral characteristics vary across the PWNe, and note that more data will place better constraints on possible thermal emission in these remnants. The imaging portion of these studies has revealed intriguing large-scale morphologies for CTB 87 and G63.7+1.1, as well as a torus-jet structure in CTB 87 and neutron star candidates in both CTB 87 and G63.7+1.1. We conclude that both CTB 87 and G63.7+1.1 are likely interacting with the supernova remnant reverse shock, and CTB 87 may be additionally influenced by the motion of its neutron star.

This Thesis describes the development of hard X-ray zone plates intended for focusing radiation at X-ray free-electron lasers (XFELs). XFELs provide unprecedented brightness and zone plates which are put in the intense X-ray beam are at risk of being damaged. Therefore, it is crucial to perform damage tests in order to design zone plates which can survive the XFEL beam. Zone plates are diffractive nanofocusing optics and are regularly used at high brightness synchrotron beamlines in the soft and hard X-ray regime. The resolution of a zone plate is proportional to its outermost zonewidth and thus depends on the smallest feature that can be fabricated. State-of-the-art nanofabrication processes developed for zone plates are able to produce zonewidths down to 10 nm. However, for hard X-rays, the zone plates need to be of sufficient thickness to efficiently focus the radiation. Thus, the limit in the fabrication of hard X-ray zone plates lies in the high aspect-ratios. This Thesis describes two processes developed for high aspect-ratio nanostructuring. The first process uses tungsten as diffractive material. Aspect-ratios up to 1:15 have been accomplished. Furthermore, a mounting method of a central stop directly on the zone plate is also presented. The other fabrication process uses diamond, in which aspect-ratios of 1:30 have been demonstrated. Both processes rely on thin-film deposition techniques, electron-beam lithography, and reactive ion etching. Thanks to the materials’ excellent thermal properties these types of zone plates should be suitable for XFEL applications. Tungsten and diamond diffractive optics have been tested at an XFEL at Stanford (LCLS), and damage investigations were performed in order to determine the maximum fluence that could be imposed on the optics before degradation occured. The conclusion of these damage tests is that tungsten and diamond diffractive optics can survive the XFEL beam and could potentially be used in beamline experiments relying on nanofocused X-ray beams. Finally in this Thesis, characterization of two zone plates using an interferometer is presented, where it is also shown that the interferometric method can be used to pin-point beamline instabilities. / <p>QC 20150112</p>

The ability to quickly and accurately quantify the plutonium (Pu) content in pressurized water reactor (PWR) spent nuclear fuel (SNF) is critical for nuclear forensics purposes. One non-destructive assay (NDA) technique being investigated to detect bulk Pu in SNF is measuring the self-induced x-ray fluorescence (XRF). Previous XRF measurements of Three Mile Island (TMI) PWR SNF taken in July 2008 and January 2009 at Oak Ridge National Laboratory (ORNL) successfully illustrated the ability to detect the 103.7 keV x ray from Pu using a planar high-purity germanium (HPGe) detector. This allows for a direct measurement of Pu in SNF. Additional gamma ray and XRF measurements were performed on TMI SNF at ORNL in October 2011 to measure the signal-to-noise ratio for the 103.7 keV peak. Previous work had shown that the Pu/U peak ratio was directly proportional to the Pu/U content and increased linearly with burnup. However, the underlying Compton background significantly reduced the signal-to-noise ratio for the x-ray peaks of interest thereby requiring a prolonged count time. Comprehensive SNF simulations by Stafford et al showed the contributions to the Compton continuum were due to high-energy gamma rays scattering in the fuel, shipping tube, cladding, collimator and detector1. The background radiation was primarily due to the incoherent scattering of the 137Cs 661.7 keV gamma. In this work methods to reduce the Compton background and thereby increase the signal-to-noise ratio were investigated. To reduce the debilitating effects of the Compton background, a crystal x-ray spectrometer system was designed. This wavelength-dispersive spectroscopy technique isolated the Pu and U x rays according to Bragg's law by x-ray diffraction through a crystal structure. The higher energy background radiation was blocked from reaching the detector using a customized collimator and shielding system. A flat quartz-crystal x-ray spectrometer system was designed specifically to fit the constraints and requirements of detecting XRF from SNF. Simulations were performed to design and optimize the collimator design and to quantify the improved signal-to-noise ratio of the Pu and U x-ray peaks. The proposed crystal spectrometer system successfully diffracted the photon energies of interest while blocking the high-energy radiation from reaching the detector and contributing to background counts. The spectrometer system provided a higher signal-to-noise ratio and lower percent error for the XRF peaks of interest from Pu and U. Using the flat quartz-crystal x-ray spectrometer and customized collimation system, the Monte Carlo N-Particle (MCNP) simulations showed the 103.7 keV Pu x-ray peak signal-to-noise ratio improved by a factor of 13 and decreased the percent error by a factor of 3.3.

The x-ray atomic form-factor determines the x-ray optical properties of materials and is a fundamental parameter for critical x-ray investigations. However, despite uncertainty estimates of order 1%, differences of 2-10% between x-ray mass attenuation measurements render comparison with the various theoretical tabulations meaningless. Moreover, such uncertainties impose limits on the accuracy of various quantitative investigations. We determine the imaginary component of the atomic form-factor from measurements of the x-ray mass attenuation coefficient. With the exception of the measurements of Tran et.al. [Phys. Rev. A 64, (062506); 67, (042716); J. Phys. B 38, (89)] with a 0.3% accuracy, previous work has been unable to achieve accuracies below 1%, and differences between results claiming this accuracy often exceed 6%.We have developed a full-foil mapping technique which has improved the measurement accuracy by an order of magnitude. This technique overcomes limitations arising from absorber thickness variations, using the average integrated column density and attenuation measurements across the entire surface of the absorber. We have examined measurements obtained over a wide range of parameter space for systematic deviations indicative of experimental error. Among others, this has led to the identification and correction of a 1% discrepancy arising from the x-ray bandwidth. Resulting measurement accuracies for molybdenum are 0.02-0.15%. Preliminary results for tin suggest a final accuracy of 0.1-1%. We compare these measurements with several commonly-used tabulations and identify a number of systematic discrepancies whose causes are discussed.

Diss. (sammanfattning) Linköping : Univ., 2001. / Härtill 5 uppsatser.

Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xx, 198 p.; also includes graphics (some col.). Includes bibliographical references (p. 191-198). Available online via OhioLINK's ETD Center.

The advances achieved using X-ray Free Electron Lasers such as the Linac Coherent Light Source (LCLS), have revolutionised the routine production of uniform solid-density plasmas. Pulses of X-rays above 1 keV and with durations shorter than 100 fs attaining intensities on target of around 10¹⁷ Wcm^-2 are now routinely created. Through simple single-photon photoionization events with atoms in ambient solid conditions, it is possible to create uniform samples that are simultaneously hot, dense, and highly ionized which may be easily modelled. This thesis describes measurements of the spectrally-resolved X-rays emitted from solid-density magnesium targets of varying sub-&mu;m thicknesses isochorically heated by an X-ray laser. The data exhibit a thickness-independent source function, allowing the extraction of a measure of the opacity to K-shell X-rays within well-defined regimes of electron density and temperature, extremely close to Local Thermodynamic Equilibrium conditions by fitting to the simple 1D slab solution of the equation of radiative transfer. The deduced opacities at the peak of the K-&alpha; transitions of the ions are consistent with those predicted by detailed atomic-kinetics calculations. The extracted opacities transpire to be robust to a plethora of variations in X-ray drive conditions, including the shape, pulse-length, and energy content. Furthermore the approximations in using the 1D slab solution are examined in detail and found to be good. A full three-dimensional model of the plasma is advanced which includes attenuation, line-of-sight effects, full longitudinal and transverse gradients, and photon time-of-flight effects. The results from this model are found to also agree with the simpler 1D slab solution. This novel method of elucidating opacities may complement other methods based on absorption and could be important for further benchmarking of opacities in solar-interior relevant conditions.