Dans le cadre de cette thèse, une technique de diagnostic optique a été développée pour mesurer simultanément l’évaporation différentielle, la distribution de température, et la concentration massique de fuel dans un jet multi-composant. Cette technique a été examinée dans les conditions d’un moteurs essence. La technique de mesure est basée sur l’utilisation des deux traceurs excités par une seule longueur d’onde.Pour pouvoir examiner l’évaporation différentielle d’un carburant multi-composant, deux traceurs ont été sélectionnés : le p-difluorobenzène et le 1-methylnaphtalène. Ces traceurs reproduisent deux types de volatilité : faible et moyenne à élevée. Les traceurs choisis fluorescent dans deux régions spectrales distinctes ce qui rend l’application de cette technique possible. Une étude photophysique a été menée pour caractériser les deux traceurs, indépendamment puis en mélange, pour différentes conditions de pression, température, et composition du bain gazeux. L’étude photophysique est essentielle pour pouvoir mesurer quantitativement l’évaporation différentielle. Les résultats photophysiques montrent que le spectre du 1-methylnaphthalène est sensible à la température. Cette caractéristique permet de mesurer la distribution en température dans le jet.Les essais ont été réalisés dans une cellule haute pression / haute température, ca-pable de simuler les conditions d’un moteur thermique. Des sprays générés par un injecteur ECN Spray G et un piézo-électrique d’une ouverture annulaire ont été étudiés. Des mesures initiales ont été menées avec chaque traceur pour pouvoir fixer la proportion de mélange des traceurs. La précision de la méthode de mesure a été calculée suivant une configuration de filtres identiques. Ensuite, les champs de tempé-rature calculés par la LIF et ceux déterminés depuis les champs de concentration massique, ont été comparés. Les résultats démontrent que la température est homo-gène ce qui signifie que les mesures d’évaporation différentielle n’ont pas influencé par la distribution de température dans le jet.Les images obtenues en détectant les signaux depuis le mélange de traceurs ont permis de localiser l’évaporation différentielle. Une variation en distribution spatiale des composants est observée 550–600 K. Cet effet disparaît en augmentant la température, ce qui explique que l’évaporation est plus rapide à haute température. La localisation de l’évaporation différentielle varie avec le type d’injecteur. La géométrie du nez ainsi que la structure du jet a donc un impact sur la formation du mélange. / A non-intrusive quantitative laser-induced fluorescence (LIF) technique capable of simultaneously measuring preferential evaporation, temperature distribution, and fuel-mass concentration across a multi-component vaporized spray has been developed and investigated under engine-relevant conditions. The measurement technique is based on two-tracer LIF with single wavelength excitation.To assess preferential evaporation, a tracer pair with suitable co-evaporation and spectral properties was selected based on vapor-liquid equilibrium calculations repre-sentative for gasoline fuels. Evaporation studies have shown that one tracer (p-difluoro-benzene) co-evaporates with the high-to-medium-volatility end of the multi-component fuel while the other (1-methylnaphthalene) co-evaporates with the low-volatility end. For quantitative measurements the photophysical properties of both tracers (each tracer separately and the combined tracers) were determined under a wide range of pressure, temperature, and bath-gas composition conditions. 1-methylnaphthalene LIF shows a strong red-shift with temperature which enables measurements of the temperature distribution across the spray.Spray evaporation and vapor mixing experiments were performed in a high-pressure high-temperature vessel capable of simulating in-cylinder conditions. An ECN Spray-G and a piezo-electric outward opening injector were used in this study. Initial measure-ments were carried out with each tracer added separately to the fuel to assess signal cross-talk and to determine the best tracer concentrations. Once the proportions were determined, accuracy and precision of the method were determined from the LIF-signal ratio of spray images within identical spectral bands. Temperature fields, obtained by two-color 1-methylnaphthalene LIF and derived from fuel concentration maps based on the assumption of adiabatic evaporation, were examined for inhomogeneities in the area of interest since fluctuations potentially influence the two-color method. It was shown that the temperature is homogeneous in the measurement volume.To localize preferential evaporation, two-color two-tracer LIF images were evaluated. Taking into account the measurement accuracy and precision, variations in the spatial distribution of the fuel volatility classes were observed for 550–600 K. At higher tem-peratures, the effect is less pronounced, which is consistent with the fact that evapora-tion is faster. The localization of preferential evaporation varied with each injector used indicating the impact of injector nozzle geometry and jet structure on mixture formation. / Eine berührungsfreies quantitatives Verfahren auf Basis von laserinduzierter Fluoreszenz (LIF) wurde entwickelt, um simultan präferenzielle Verdampfung, Temperaturverteilung und Kraftstoffkonzentration im verdampften Bereich eines Mehrkomponenten-Kraftstoffsprays unter motorrelevanten Bedingungen zu messen. Verfahren beruht auf Zwei-tracer-LIF mit Anregungmit einem Laser.Es wurde ein Tracer-Paar mit geeigneten Verdampfungs- und spektralen Eigenschaften auf Basis von Dampf-Flüssigkeits-Gleichgewichtsrechnungen für Otto-Kraftstoffe ausgewählt. Verdampfungsmessungen haben gezeigt, dass ein Tracer (p-Difluorbenzol) gleichzeitig mit dem mittel- und höherflüchtigen Siedeklassen verdampft, während der andere (1-Methylnaphthalin) den schwerflüchtigen Komponentenfolgt. Für quantitative Messungen wurden die photophysikalischen Eigenschaften beider Tracer (einzeln und als Kombination) in einem weiten Bereich von Druck, Temperatur und Gaszusammensetzung bestimmt. 1-Methylnaphthalin-LIF zeigt eine starke Rotverschiebung mit der Temperatur, die Messungen der Temperaturverteilung ermöglicht. Es wurde ein Tracer-Paar mit geeigneten Verdampfungs- und spektralen Eigenschaften auf Basis von Dampf-Flüssigkeits-Gleichgewichtsrechnungen für Otto-Kraftstoffe ausgewählt. Verdampfungsmessungen haben gezeigt, dass ein Tracer (p-Difluorbenzol) gleichzeitig mit dem mittel- und höherflüchtigen Siedeklassen verdampft, während der andere (1-Methylnaphthalin) den schwerflüchtigen Komponentenfolgt. Für quantitative Messungen wurden die photophysikalischen Eigenschaften beider Tracer (einzeln und als Kombination) in einem weiten Bereich von Druck, Temperatur und Gaszusammensetzung bestimmt. 1-Methylnaphthalin-LIF zeigt eine starke Rotverschiebungmit der Temperatur, die Messungen der Temperaturverteilung ermöglicht.

Single enzymes of E. coli sourced B-galactosidase were analysed in effort to expand the wealth of knowledge in the area of heterogeneity. Static and dynamic heterogeneity was studied with respect to catalytic rate, electrophoretic mobility, and heat shock protein chaperone systems. Temperature was found to be a contributing factor to the observed range of dynamic heterogeneity, with the range increasing with temperature. The inhibitor dissociation constant was determined to be a heterogeneous property of B-galactosidase. A novel assay was developed in which a single enzyme molecule was subjected to three separate solutions while the enzyme itself remained free in solution. / October 2016

Doctor of Philosophy / Department of Chemistry / Ryszard J. Jankowiak / Low-temperature laser-induced fluorescence spectroscopy has various applications in analytical, physical, and biophysical chemistry. This technique provides information on the fluorescence origin band, zero-phonon lines and phonon-sidebands, inhomogeneous broadening, electron-phonon coupling strength, and ground- and excited-state vibrational frequencies of studied molecules. Examples discussed in this work include studies of DNA/metabolites and monoclonal antibody (mAb)/antigen interactions. The structural basis for the increased reactivity of BPDE towards guanines at 5-methylcytosine ([superscript]M[superscripte]eC):G sites in DNA was investigated by low temperature laser-based spectroscopy, studying the nature of physical complexes of benzo[a]pyrene tetraol in a series of 5-methylcytosine structural DNA analogs. We found that the presence of a C-5 substituent on cytosine and related structural modifications influences the conformation of BPT in DNA analogs, and could explain the increase in guanine reactivity at [superscript]M[superscript]eC:G sites of the p53 tumor suppressor gene that contains endogenenous 5-([superscript]M[superscript]eC. It has been demonstrated that various mAbs can bind a particular cross-reactant by adopting two distinct "red" and "blue" conformations of its binding sites. We showed that the blue conformation of pyrene in several mAbs (including 4D5 mAb) is consistent with [pi]-cation interactions, underscoring the importance of [pi]-cation interaction in ligand binding. We propose that considerable narrowing of the fluorescence origin band of the ligand in the protein environment could be regarded as a simple indicator of [pi]-cation interactions. It is also shown that time-resolved delta fluorescence line-narrowing ([delta]FLN) spectroscopy, using excitation within the (0,0)-transition band, provides more reliable information of the frequency dependence of the electron-phonon coupling (Huang-Rhys factor, (S < 1). Finally, analytical formulas were developed to describe FLN spectra with excitation energy transfer present. Our calculated FLN spectra are compared with spectra obtained by a simple convolution method (SC) and a more rigorous treatment using Redfield theory. We demonstrate that, under the condition of weak coupling between pigments (i.e., the coupling constant is smaller than the reorganization energy) and weak electron-phonon coupling strength (S < 1), our analytical formulas provide an excellent approximation of the SC and Redfield methodologies. We argued that our approach could also model FLN spectra obtained for very complex biological systems.

In this thesis 3D diamond detectors were fabricated using an ultrafast femtosecond (120 fs) pulse length laser, with a 800nm wavelength, to induce a phase change of diamond to graphite to form electrodes in the diamond bulk. Graphitic electrodes, with diameters of O(um), were fabricated using a known processing technique and were enhanced further through the use of a Spatial Light Modulator (SLM), which is a new technology in this field. These detectors were subsequently characterised through the use of particle beams, and this work also presents methods for characterising such detectors: A pair of crossed polarisers to determine the stress induced by the electrodes on the diamond bulk; Raman spectroscopy to assess the relative quantity of diamond:graphite formed; Scanning Electron Microscopy (SEM) to image the starting (seed) and finishing (exit) sides of electrode formation; and current-voltage (I-V) measurements to calculate the electrical properties of the electrodes. These characterisation methods (alongside the use of particle beams) serve as a means to compare the two fabrication techniques and to determine the optimum fabrication parameters to produce 3D diamond detectors for use as tracking detectors in high luminosity environments such as those in the Large Hadron Collider (LHC). This work shows that using a higher beam energy and translation speed of the focal spot results in electrodes of lower electrical resistivity, which is an ideal characteristic for a tracking detector. These higher processing parameters also result in more graphitic structure on the seed and exit sides of the diamond, determined separately via Raman spectroscopy and SEM. An increased beam energy also results in larger electrode diameters, reducing the active area of the detector and inducing more stress in the diamond bulk. These measurements therefore indicate an upper limit on the fabrication parameters. A further study into these processing parameters shows the translation speed scales with the pulse repetition rate of the laser and allows for fast fabrication of 3D diamond detectors. Two devices were fabricated with and without the use of an SLM, with a more uniform detector response (through characterisation by particle beams), lower electrical resistivity, and more graphitic material observed for SLM-fabricated electrodes. The benefits of square and hexagonal cell structures were also investigated with both structures showing a similar response to particle beams. A lower charge sharing region is observed in hexagonal cells and indicates potentially different applications for these cell geometries. Transient Current Technique (TCT) measurements were also taken on both detectors, where faster charge collection and higher quality data were seen for the SLM-fabricated device. These measurements indicate a preference in the use of an SLM for the future fabrication of 3D diamond tracking detectors. These TCT measurements were then compared to simulations to extract the charge carrier properties in diamond. Only qualitative agreement was obtained, motivating further work in this area to fully understand the charge carrier dynamics and demonstrate the future viability of 3D diamond detectors.

Nuclear plant stainless steel can become contaminated by radionuclides during normal operation whereby the final disposition of these materials then becomes a major decommissioning challenge to address. Characterisation of the chemical and metallurgical processes that underpin contamination is essential in consideration of developing cost effective decontamination and prevention methods, as are in situ measurement techniques that allow assessment of contamination. To address these issues, contamination experiments to simulate the nitric acid-based reprocessing streams of the PUREX (Plutonium Uranium Redox Extraction) process, and alkaline spent fuel storage ponds were investigated. Solution and surface spectroscopic measurements were performed to characterise the sorption behaviour of stable analogues of two high yield fission products, Sr-90 and Cs-137, on as received and 30 % cold rolled AISI Type 304 stainless steel, respectively. In addition Laser Induced Breakdown Spectroscopy (LIBS) was also investigated as a standoff contamination assessment technique. Fission product accumulation was modelled to a second order kinetic fit that considers chemisorption, typically to a hydrous metal oxide surface, as rate controlling. This process is observed to be independent of solution composition and strain processing regime. This behaviour reflects complexation to the passivating surface chromium oxide film, and as determined by depth elemental analysis, effectively inhibits contaminant migration into the bulk material. Environment chemistry and microstructural variables that destabilise the Cr-rich passive film however reduces the passive layer capabilities to effectively inhibit fission product bulk diffusion. The importance of corrosion phenomena towards radionuclide sorption processes necessitates the consideration of metallurgical and chemical factors during the implementation of decontamination approaches to treat affected plant material at nuclear licenced sites. LIBS was found to be a satisfactory technique for measurement of Sr sorbed to steel but Cs could not be detected at the concentrations used in this experimentation. Furthermore, EDX and TOF-SIMS elemental mapping indicated ablated material may be redistributed into the crater profile during elemental analysis. This process has clear implications for the deployment of LIBS for in situ characterisation of nuclear materials as the uncontrolled redistribution of radioactive material certainly violates decommissioning principles.

No description available.

The practical application of non-photochemical laser-induced nucleation (NPLIN) to continuous flow was investigated. Supersaturated aqueous solutions were screened with a 5 ns pulsed laser (532 nm 44 MW cm-2) for NPLIN activity. Upon irradiation succinic acid nucleated at S20 = 4.3 and adipic acid at S20 = 2.0 - 3.0. NPLIN activity is reported for the first time in nicotinic acid (S20 = 2.6 - 3.0). No overall pattern was observed of chemical structure on NPLIN activity. From inorganic compounds similarly screened, ammonium chloride (S20 = 1.04 - 1.20) was identified as most suitable for further tests. It was shown to have an increase of NPLIN crystals with higher supersaturation from 13 at S = 1.038 to 252 at S = 1.135. A quadratic increase in number of crystals with increased laser power. The effects of NPLIN upon ammonium chloride are diminished upon filtration through a 0.2 μm poly (ether sulfone) filter, reducing the number of crystals from 350 to 10 per 70 mJ pulse (25 MW cm-2). The use of NPLIN in continuous flow was demonstrated from the first time. A S23 = 1.1 solution of aqueous ammonium chloride in flow produced crystals when irradiated by 10 pulses s-1 of a 1064 nm 6 ns laser. When the laser was stopped, crystals were no longer produced and the system returned to flowing supersaturated solution. Lab scale apparatus for continuous NPLIN experiments was developed. A design involving a re-dissolution step and loop flow was constructed for both laminar and slug-flow regimes. Nucleation of ammonium chloride (S = 1.1) was demonstrated in both systems. Repeatable NPLIN experiments were hindered by spontaneous nucleation. Spontaneous nucleation in flow was observed around areas where supersaturated solution passed from one component to another. Spontaneous nucleation was also observed upon cooling (25 to 10 °C). Filtration was observed to both suppress NPLIN and spontaneous nucleation in flow.

The performance of an inductively coupled plasma mass spectrometer, ICP-MS, depends on the instrument's ability to transport sample ions through the vacuum interface and focus the ions into a well-defined beam that will eventually reach the mass analyzer. In this study two main experiments were performed on the Perkin Elmer NexION 300S, a commercial ICP-MS. First, planar laser-induced fluorescence images were taken of the ion beam in a working instrument downstream from a unique quadrupole ion deflector. The images showed the ability of the instrument design to focus the ions in the ion beam. Second, laser-induced fluorescence was used to characterize ion flow through the vacuum interface. The interface is unique to the NexION ICP-MS in that there are three extraction cones. The effect of a three-cone interface on ideal skimming is discussed.

In this thesis, two different experimental approaches to capacitive deionization (CDI) process are presented. In the first approach, transient system characteristics were analyzed to find three different operating points, first based on minimum outlet concentration, second based on maximum average adsorption rate and third based on maximum adsorption efficiency. These three operating points were compared in long term desalination tests. In addition, the effects of inlet stream salinity and CDI system size have been characterized to assess the feasibility of a commercial CDI system operating at brackish water salinity levels. In the second approach, the physical phenomena occurring inside a capacitive deionization system were studied by laser-induced fluorescence visualization of a “pseudo-porous” CDI microstructure. A model CDI cell was fabricated on a silicon-on-insulator (SOI) substrate and charged fluorophores were used to visualize the simultaneous electro migration of oppositely charged ions and to obtain in situ concentration measurements. / text

A new diagnostic technique for studying the turbulent mixing characteristics of supersonic mixing flowfields is developed and implemented in two Mach 3 mixing flowfields. The diagnostic utilizes simultaneous particle image velocimetry and quantitative planar laser-induced fluorescence of krypton gas to study the interaction between turbulent scalar and velocity fields. The fluorescence properties of krypton gas are determined; measurements of the pressure and temperature dependence of the collisional quenching rates and cross-sections are made for various mixtures with krypton. The gases tested in this fashion include helium, nitrogen, air, oxygen, and ethylene. Additional measurements are performed to measure the relative two-photon absorption cross-section for krypton gas. The non-dimensional quenching rates are found to follow a power-law dependence for temperature, while the pressure dependence of the total quenching rate is found to be linear. Two injection flowfields are studied for their general topology and kinematic characteristcs. The first injector model is a basic injector meant to serve as a baseline case; there are no hypermixing elements present in this model. The second model is an asymmetric, unswept hypermixing injector featuring 15 degree expansive ramps flanking a central block. These studies utilize particle image velocimetry in planar and stereoscopic configurations in various planes. Results for the mean flowfield show distinct differences between the two flowfields; the planar injector flowfield is shown to be highly two-dimensional and exhibits minimal coherent unsteady behavior. The hypermixing injector flowfield exhibits a highly three-dimensional wake, with a pair of stream-wise vortices driving both mean deviations in the flowfield and considerable vortical coupling in the span-wise direction. Simultaneous krypton PLIF and PIV are employed in the two mixing flowfields. An assay of the dependence of the krypton mole fraction calculations on the fluorescence signal is performed. The overall sensitivity and the resulting dynamic range of the calibration is dictated largely by the reference mole fraction. Additionally, several different theoretical models of the temperature dependence of the fluorescence signal are studied to assess their validity and influence over the PLIF calibration procedure. Finally, the technique is employed in the two mixing flowfields, and a brief analysis of the mean and unsteady behavior of the two is conducted. / text