<div>Laser-absorption spectroscopy (LAS) is widely used for providing non-intrusive and quantitative measurements of gas properties (such as temperature and absorbing species mole fraction) in combustion environments. However, challenges may arise from the line-of-sight nature of LAS diagnostics, which can limit their spatial resolution. Further, time-resolution of such techniques as scanned direct-absorption or wavelength-modulation spectroscopy is limited by the scanning speed of the laser and the optical bandwidth is often limited by a combination of a laser's intrinsic tunability and its scanning speed. The work presented in this dissertation investigated how recent advancements in mid-IR camera technology and lasers can be leveraged to expand the spatial, temporal, and spectral measurement capabilities of LAS diagnostics. Novel laser-absorption imaging and ultrafast laser-absorption spectroscopy diagnostics are presented in this dissertation. In addition, the high-pressure combustion chamber (HPCC) and high-pressure shock tube (HPST) were designed and built to enable the study of, among others, energetic material combustion, spectroscopy, non-equilibrium and chemistry using optical diagnostics.<br></div><div><br></div>

Nuclear energy can be used to reliably generate large quantities of electricity while providing minimal lifetime CO2 emissions. Given the extreme importance of safety in the nuclear industry, it is necessary to have a fundamental understanding of the materials used throughout the nuclear fuel cycle. It is of particular to importance to develop an understanding of these materials at an atomic level. In this thesis, X-ray absorption spectroscopy (XAS), along with several other X-ray based techniques, has been used to study materials that are produced or proposed for use in the nuclear fuel cycle. Uranium mining and milling operations generate large quantities of waste, known as mine and mill tailings. At their McClean Facility in Northern Saskatchewan, AREVA Resources Canada disposes of the tailings waste using the JEB Tailings Management Facility (TMF). AREVA monitors the mineralization of elements of concern (i.e., Ni, As, Fe, Mo, Ra, and U) within the TMF as part of its on-going commitment towards managing the facility’s environmental impact. Molybdenum (Mo) is predicted to mineralize as insoluble powellite (CaMoO4) within the TMF. However, no experimental evidence confirmed the presence of powellite in the TMF. In Chapter 2, the presence of powellite, and other Mo-bearing minerals, was determined using powder X-ray diffraction (XRD), X-ray fluorescence imaging, and Mo K-edge XAS. The results of this study confirmed that powellite was present in the TMF and showed that Mo K-edge XAS was the only effective way to detect the Mo minerals within the TMF. New materials for use as nuclear fuels were also investigated in this thesis. Spent nuclear fuel must be securely stored for long periods of time due to the presence transuranic elements (TRU; i.e., Pu, Am, Np, Cm), and the use of inert matrix fuels (IMF), which consist of actinides embedded in a neutron transparent (inert) material, have been proposed for to “burn-up” or transmute these TRU species. Stabilized ZrO2 materials have been proposed for use in IMF applications, and in Chapter 3 the thermal stability of a series of NdxYyZr1-x-yO2-\delta materials made by a ceramic synthetic route have been studied using powder XRD, scanning electron microscopy (SEM), and X-ray absorption spectroscopy. (Nd was used as a surrogate for Am.) The results of this study showed that the fluorite structure of the NdxYyZr1-x-yO2- \delta materials was stabilized when y >= 0.05, and that the local environment around Zr was independent of composition or annealing temperature. The effect of synthetic method on the thermal stability of the NdxYyZr1-x-yO2-\delta materials was also determined, and this is the subject of Chapter 4. In this study a series of NdxY0.25-xZr0.75O1.88 materials were synthesized using a low-temperature co precipitation synthesis, and these then annealed at 1400 °C and 1500 °C. The as-synthesized and annealed materials were characterized by powder XRD, SEM, and XAS. This study confirmed that the thermal stability of the materials was dependent on synthetic method, and that materials made using a solid-state method were superior to those produced by a solution-based approach. Y-stabilized zirconia has a low thermal conductivity, which is not ideal for a nuclear fuel. The thermal conductivity could be increased if a lighter cation, such as Sc, was used to stabilize the fluorite structure. In Chapter 5, the thermal stability of a series of NdxScyZr1-x-yO2-\delta materials was investigated. The as-synthesized and annealed materials were studied by powder XRD, SEM, and XAS. These results showed that the fluorite structure was only stable in the annealed materials when x+y >= 0.15 and y >= 0.10. The results of this study provided insight into the possible use of scandia-stabilized zirconia for use as an inert matrix fuel. This studies presented in this thesis have used X-ray absorption spectroscopy and a number of other techniques to characterize materials important to the nuclear fuel cycle. The studies presented here were only possible because of the unique information that can be obtained using XAS. This thesis serves to highlight the importance of XAS as a technique and how it can be applied to solve problems related to the material science of the nuclear fuel cycle.

The Gram-positive pathogens Corynebacterium diphtheriae and Streptococcus pyogenes both require iron for survival. These bacteria have developed sophisticated heme uptake and transport protein machinery responsible for the import of iron into the cell, in the form of heme from the human host. The heme utilization pathway (hmu) of C. diphtheriae utilizes multiple proteins to bind and transport heme into the cell. One of these proteins, HmuT, delivers heme to the ABC transporter HmuUV. The axial ligation of the heme in HmuT was probed by examination of wild-type HmuT and a series of conserved heme pocket residue mutants, H136A, Y235A, R237A, Y272A, M292A, Y349A, and Y349F. Characterization by UV-visible absorption, resonance Raman, and magnetic circular dichroism spectroscopies indicated that H136 and Y235 are the axial ligands in HmuT. Electrospray ionization mass spectrometry was also utilized to assess the roles of conserved residues in contribution to heme binding. The S. pyogenes streptococcal iron acquisition (sia)/heme transport system (hts) utilizes multiple proteins to bring host heme to the intracellular space. Both the substrate binding protein SiaA and the hemoprotein surface receptor Shr were investigated. The kinetic effects on SiaA heme release were probed through chemical unfolding of axial ligand mutants M79A and H229A, as well mutants thought to contribute to heme binding, K61A and C58A, and a control mutant, C47A. The unfolding pathways showed two processes for protein denaturation. This is consistent with heme loss from protein forms differing by the orientation of the heme in the binding pocket. The ease of protein unfolding is related to the strength of interaction of the residues with the heme. Shr contains two NEAT (near-iron transporter) domains (Shr-N1 and Shr-N2) which can both bind heme. Biophysical studies of both Shr-N1 and Shr-N2 indicated a new class of NEAT domains which utilize methionine as an axial ligand, rather than a tyrosine. Thermal and chemical unfolding showed ferrous Shr-N1 and Shr-N2 to be most resistant to denaturation. Shr-N2 was prone to autoreduction. Together, sequence alignment, homology modeling, and spectral signatures are all consistent with two methionines as the heme ligands of this novel type of NEAT heme-binding domain.

Understanding the fundamental electronic properties of materials is a key step to develop innovations in many fields of technology. For example, this has allowed to design molecular based devices like organic field effect transistors, organic solar cells and molecular switches. In this thesis, the properties of advanced functional materials, in particular metal-organic molecules and molecular building blocks of 2D materials, are investigated by means of Density Functional Theory (DFT), the GW approximation (GWA) and the Bethe-Salpeter equation (BSE), also in conjunction with experimental studies. The main focus is on calculations aiming to understand spectroscopic results. In detail, the molecular architectures of lutetium-bis-phthalocyanine (LuPc2) on clean and hydrogenated vicinal Si(100)2×1, and of the biphenylene molecule on Cu(111) were analysed by means of X-ray Photoelectron spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy; DFT calculations were performed to obtain insights into the atomic and electronic structures. Furthermore, detailed information about the electronic states of the gas phase iron phthalocyanine (FePc) and of the gas phase biphenylene molecule were obtained through XPS and NEXAFS spectroscopy. I have studied by means of DFT, multiplet and GWA calculations the electronic correlation effects in these systems. Also the optical, electronic and excitonic properties of a hypothetical 2D material based on the biphenylene molecule were investigated by GWA and BSE calculations. Monolayers of metal-free phthalocyanine (H2Pc) on Au(111) and of FePc on Au(111) and Cu(100)c(2×2)-2N/Cu(111) with and without pyridine modifier were studied by XPS and final state calculations. A multiplet approach to compute L-edges employing the hybridizations function, known from dynamical mean field theory, was proposed and applied to transition metal oxides.

Thesis (MSc (Physics))--University of Stellenbosch, 2009. / In the presented study a diode laser was characterised and used for spec- troscopy, measuring the resonance lines of atomic rubidium. The characteristics of diode lasers and external cavity diode lasers (ECDL) for the purposes of ab- sorption spectroscopy were investigated and an experimental setup for tunable diode laser spectroscopy using an ECDL was developed. In external cavity diode lasers, the advantages of low cost, small size and e ciency of a diode laser is combined with tunability and a narrow frequency bandwidth. The ECDL was applied in experimental setups for absorption spectroscopy and saturated ab- sorption spectroscopy. Measurement of the absorption of atomic rubidium's D2 line near 780 nm is discussed. The Doppler broadened, as well as the Doppler free spectrum of the ne and hyper ne structure of the D2 line were measured and is discussed. Finer control of the ECDL's stability and frequency, using a servo circuit, were investigated and tested. An overview is given of laser cool- ing and trapping of neutral rubidium atoms, which is the main application the ECDL were developed for.

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The large band gap (approximately 11.5-12.1 eV) and high transmission of calcium fluoride (CaF2) crystal in the ultraviolet (UV) and vacuum ultraviolet (VUV) region makes it an important material for optics for laser applications in UV. However, CaF2 degrades during long exposure to UV irradiation due to defect generation. The formation of selftrapped excitons (STE) is considered the first step in defect generation. In this project the possibility of observing STE states in CaF2 using a narrow bandwidth tunable VUV laser source is investigated. This is the first spectroscopy study of an alkaline earth fluoride using VUV tunable laser radiation instead of a fixed wavelength laser. The use of a VUV tunable laser source has potential for determining the energies of the STE states, which are unknown. Our main objective is addressed by developing techniques to measure absorption spectra of pure and doped CaF2 samples, using a VUV scanning monochromator and a tunable VUV laser, and by doing a literature study. The results obtained with the scanning monochromator show absorption features in 126-180 nm range of all our samples. These vary for different samples and correlate with information from the supplier on the samples’ fluorescence spectra. Total absorption of the VUV light by CaF2 in the 115-126 nm range is observed. With the narrow bandwidth tunable laser light, absorption spectra were obtained in the range of 143-146.7 nm of all our CaF2 samples. No significance peaks which can be related to the STE states in CaF2 were observed in the VUV laser absorption spectra, but the results are valuable to improve the technique. The conclusion is that either a different spectral range or fluorescence detection can be investigated in future. / AFRIKAANSE OPSOMMING: Die groot bandgaping (ongeveer 11.5-12.1 eV) en hoë transmissie van kalsiumfluoried (CaF2) kristal in die ultraviolet (UV) en die vakuum ultraviolet (VUV) gebied maak dit ’n belangrike materiaal vir optika vir laser toepassings in die UV. CaF2 degradeer egter gedurende langdurige blootstelling aan UV lig as gevolg van die generering van defekte. Die vorming van ’n elektron-holte paar wat deur die kristalstuktuur gestabiliseer word teen rekombinasie (self-trapped excitons, afgekort STE) word beskou as die eerste stap in defek generering. In hierdie projek word die moontlikheid ondersoek om STE toestande in CaF2 waar te neem deur die gebruik van ’n afstembare VUV laserbron met emissie in ’n smal spektrale band. Dit is die eerste spektroskopiese studie van ’n aardalkali-fluoried deur die gebruik van afstembare VUV laserlig in plaas van ’n vaste golflengte laser. Die gebruik van ’n afstembare VUV laserbron het potensiaal vir die bepaling van die energieë van die STE teostande, wat onbekend is. Ons hoofdoel word aangespreek deur die ontwikkeling van tegnieke vir die meet van absorpsie spektra van suiwer en gedoteerde CaF2 monsters met behulp van ’n VUV skanderende monochromator en ’n afstembare VUV laser, en deur ’n literatuurstudie. Die resultate wat behaal is met die skanderende monochromator toon die absorpsieprofiele van al ons monsters in die 126-180 nm spektrale gebied. Die absopsieprofiele varieer vir die verskillende monsters en korreleer met die inligting van die verskaffer oor die fluoressensie spektra van die monsters. Totale absorpsie van die VUV lig deur CaF2 in die 115-126 nm gebied is waargeneem. Met die smalband afstembare laserlig is absorpsie spektra in die 143-146.7 nm gebied vir al ons CaF2 monsters verkry. Geen beduidende pieke wat verband hou met die STE toestande in CaF2 is waargeneem in die VUV laser absorpsie spektra nie, maar die resultate is waardevol vir die verbetering van die tegniek. Die gevolgtrekking is dat of ’n ander spektraalgebied of fluoressensiedeteksie in die toekoms ondersoek kan word.

Cleaning validation of pharmaceutical manufacturing equipment is required by legislation. Generally, wet chemical techniques are employed using swabbing and/or rinse sampling methods. These are generally either selective and time consuming, or less selective and give results in a shorter period. The infrared reflection absorption spectroscopy (IRRAS) technique explored here attempts to deliver accurate, selective surface contamination information in real time to complement current methods and reduce down-time. The IRRAS instrument used in this research is a Fourier transform infrared (FTIR) spectrometer coupled by an IR fibre-optic cable to a grazing-angle sampling head with a fixed incidence angle of 80°. The introduced flexibility permits collection of in situ spectra from contaminated surfaces. Calibration models are developed using the multivariate, linear partial least squares (PLS) statistical method. The research focuses on sodium dodecyl sulfate (SDS), a model cleaning agent, on metal (aluminium and stainless steel) and dielectric (glass, EPDM and silicone) surfaces. The effects of surface finish are investigated for SDS on stainless steel. Calibrations for SDS and paracetamol in the presence of each other on glass surfaces are examined, as well as a common industrial cleaner (P3 cosa® PUR80) on polished stainless steel. For the calibration sets in this thesis, RMSECV values were < 0.41 µg cm⁻², corresponding to conservative surface residues detection limits of better than ~0.86 µg cm⁻². However, RMSECV values depend on the calibration loading range, and the detection limits were typically ~0.2 µg cm⁻² for loading ranges 0-2.5 µg cm⁻². These are below visual detection limits, generally taken to be 1-4 µg cm⁻², depending on the analyte and substrate. This shows that IRRAS is a viable method for the real-time detection and quantification of surface contamination by surfactants and active pharmaceutical ingredients on metals and dielectrics.

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