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 objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

CD containing a copy of the thesis, software and extra documentation is held with print copy. / Nuclear Magnetic Resonance (NMR) is a relatively complex technique and normally requires expensive equipment. However, with advances in computing, electronics and permanent magnet technologies, NMR is becoming more feasible as a non-invasive tool for industry. The strength of NMR is its ability to probe at the molecular level and hence gain information about molecular structure, organisation, abundance and orientation. This thesis describes the development of an instrumentation platform technology that is compact and therefore portable. It has been produced to aid the development of NMR based tools or sensors for research and industry and will lead to a series of low cost, portable NMR systems for the non-destructive testing of materials such as polymer composites, rubber, timber, bricks and concrete. The instrumentation is largely electronics based and consists of a series of modules that can be interconnected to produce a solution. The first of two main modules is called the system core. What is common to all NMR applications is the generation of precisely timed signals, the capturing of signals and the processing/display of data. This has been implemented by developing a general purpose Digital Signal Processor (DSP) based instrumentation and control module that uses a Universal Serial Bus interface to communicate with a host computer. A graphical user interface is provided by an application running under Windows® XP. The second main module is a radio frequency transceiver that has been developed using digital receiver technology. The signals, after some amplification, are digitized with a 14-bit, 62.5MH.z analogue to digital converter. The sampled signal is then mixed digitally with synthesized sine and cosine functions to generate lower frequency quadrature outputs which are then digitally filtered and decimated before being passed onto the DSP for further processing and storage. A direct digital synthesizer with an analogue output is used to generate any required excitation signals. All synthesizers have phase and frequency hopping capabilities and are phase locked to each other and the DSP. The system was designed to interface to a range of NMR probes. The type of probe is determined by the intended application and each probe has specific requirements such as the type of radio frequency power amplifier, duplexer and preamplifier needed. This results in a number of instrumentation variations and a modular instrument enclosure was used to cater for these variations. The instrument was first configured for an NMR probe called the NMR-MOUSE. Tests were performed with this probe to verify the correct operation and performance of the instrument. The instrument was then reconfigured for a new probe called the NMR-MOLE and further testing was performed. This probe was still undergoing development and had not been previously tested. Finally, a dedicated compact instrument measuring 360 x 240 x 55 mm and weighing 3.6 kg was developed for the NMR-MOUSE probe.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

The objective of this thesis was to develop novel technologies for measuring the physical characteristics of high-speed pulse trains, for use in performance monitoring applications. This thesis describes the development of three separate techniques that perform measurements in either the time domain, frequency domain or the phase space of the optical signal. The first section investigates phase-sensitive pulse measurement techniques. A high- resolution SHG-FROG apparatus was custom-designed to measure 40GHz RZ pulse trains, from which an operational characterisation of a Mach-Zehnder modulator (MZM) was realised. A numerical model of a nonlinear pulse compressor was developed to compress 40GHz RZ pulses from 8.5ps down to 3.4ps. These pulses were time-division multiplexed to 80GHz, and phase-retrievals of the 80GHz pulse trains were measured. A comparison between the techniques of SHG-FROG and linear spectrogram has been undertaken for 10GHz pulse sources, exposing SHG-FROG's weaknesses at this particular repetition rate. The second section investigates a simple, time-averaged, nonlinear detection technique. Two-photon absorption in a GaAs/InGaAs quantum-well laser diode was used to measure the duty cycle (and by extension, the pulse duration) of a range of pulse sources. This technique was further developed to measure the extinction ratio of NRZ pulse trains. Additionally, the pulse duration of a mode-locked laser source was measured using the nonlinear absorption in a 1-m length of As2Se3 Chalcogenide glass fiber. This demonstrates that the nonlinear properties of this glass may well find application in future instrumentation. The third section investigates the development of an ultra-high resolution swept heterodyne spectrometer. This spectrometer was used to spectrally-distinguish repetitive 8-bit NRZ patterns at 2.5Gbit/s. It was also used to measure the chirp parameter of an X-cut LiNbO3 MZM, revealing a chirp parameter of απ/2 < 0.1 across a modulation band- width of 250-2500MHz. Additionally, the distinctive CW spectrum of a DFB laser diode was measured. Analysis of the measured CW spectrum yielded a linewidth enhancement factor of α≃ 1.8 and also the relative intensity noise of the DFB laser diode.

The aim of my diploma thesis was to assess possibilities of tracing and, consequently, identifying radionuclides in transported materials detected by detection frames on the protected area border of the nuclear power plant of Temelín, by means of the portable spectrometer Inspector 1000. To achieve this, I designed a series of measurements based on a simulated passage of a motor vehicle fitted with ionizining radiation sources of various activities at the designed points of measurement so that these measurements corresponded as close as possible to the actual passage of vehicles with large-sized loads. Recorded values were analysed and marginal activities for the particular measuring points were fixed. Computation correctness was then verified by another passage of the vehicle through the measuring device. Specified values of the marginal activities at the particular measuring points were, for comparison, consequently measured by the portable spectrometer Inspector 1000. Measurement results proved that the portable spectrometer Inspector 1000 can efficiently detect, identify and locate the sources of ionizing radiation causing the alarm level to be exceeded on a stable measuring device at the fixed measuring points, with a higher sensitivity than a stable measuring device. Conclusions of this diploma thesis will be given to the radiation protection unit of the nuclear power plant of Temelín as a basis for specification or even expansion of the methods of measuring ionizining radiation sources when transporting large-sized loads in the nuclear power plant, and their introduction into the monitoring programme.

Ces dernières années, la mesure des isotopologues de l'eau est devenue de plus en plus importante pour les sciences de l'atmosphère. A cause de l'influence des conditions climatiques sur les rapports isotopiques, la composition isotopique de l'eau conservée dans la glace en Antarctique et en Arctique peut être utilisée comme un paléothermomètre permettant de comprendre les changements passés du climat. La mesure des variations de la composition isotopique de la vapeur d'eau dans l'atmosphère peut servir à étudier le cycle hydrologique global de la terre et à raffiner les modèles de circulation atmosphérique.Alors que la méthode conventionnelle pour la mesure des isotopes de l'eau, la Spectrométrie de Masse des Rapports Isotopiques (IRMS), n'est pas adaptée aux mesures en continu et in-situ des isotopes de vapeur d'eau, le développement récent des spectromètres laser offre une méthode simple et robuste pour effectuer des recherches sur le terrain avec une bonne résolution temporelle. Pourtant, jusqu'à présent la plupart des instruments optiques exigent des niveaux d'humidité relativement élevés avec des concentrations d'eau supérieures à 1000 ppmv, ce qui exclut les mesures dans quelques unes des régions les plus intéressantes pour l'investigation des variations isotopiques dans l'eau, telles que les couches élevées de l'atmosphère ou les régions centrales de l'Antarctique.Ce travail introduit un nouveau spectromètre laser infrarouge qui est basé sur la technique d'OFCEAS et qui a été conçu spécialement pour la mesure des quatre isotopologues H2_16O, H2_18O, H2_17O et HDO dans un environnement sec avec des concentrations d'eau de quelques centaines à seulement quelques dizaines de ppmv. L'instrument qui a été développé dans le cadre de cette thèse montre une stabilité de mesure supérieure comparée aux instruments OFCEAS précédents, avec des temps d'intégration optimaux pouvant aller jusqu'à plusieurs heures et une longueur de trajet optique effective de plus de 30 km.La performance globale de l'instrument est analysée et le problème de la dépendance des mesures isotopiques vis-à-vis de la concentration d'eau avec laquelle l'expérience est effectuée est investigué en détail. La présence d'un motif fixe spectral est identifiée comme la source principale de bruit et analysée en détail.En outre, un nouveau système de calibration pour des mesures d'isotopes de vapeur d'eau est présenté. Ce système a été développé dans le cadre de cette thèse afin de disposer d'un moyen fiable et stable pour la calibration des mesures des variations isotopiques de la vapeur d'eau. Le système de calibration est basé sur l'injection continue d'eau dans une chambre d'évaporation avec deux pousse-seringue au nanolitre. Il est capable de générer une vapeur d'eau standard entre 5 et 15000 ppmv. Une simulation modélisée de l'injection d'eau, qui est en bon accord avec les expériences, est présentée.Ensuite une première utilisation du spectromètre OFCEAS dans la station de recherche norvégienne (Troll) en Antarctique est exposée en détail. Les données enregistrées pendant une période de trois semaines de Février à Mars 2011 sont présentées et discutées, en particulier relativement aux problèmes de calibration rencontrés avec un système de calibration rudimentaire construit sur place. Pendant cette période le spectromètre a mesuré en continu les isotopologues de vapeur d'eau dans l'atmosphère sur le site de la station.Pour conclure, nous allons présenter le projet Isocloud, un projet international avec pour but d'étudier des effets de (super)saturation en utilisant la chambre à nuages AIDA du KIT en Allemagne. Notre spectromètre et le système de calibration faisaient partie de ce projet. Les données expérimentales de quatre campagnes de mesure sont présentées et des résultats préliminaires sont discutés. Nous concluons avec la discussion d'un protocole de mesure optimal et donnons des perspectives pour le futur. / In recent years, the measurement of water isotopologues has become increasingly important for atmospheric research. Due to the influence of climatic conditions on the isotope ratios, the isotopic composition of water stored in the ice in Antarctica and the Arctic can be used as paleothermometers to reconstruct past climate changes. The measurement of changes of the isotopic composition of water vapor in the atmosphere can be used to study the global hydrolocal cycle and to refine atmospheric circulation models.Whereas the conventional method for water isotope measurements, Isotope Ratio Mass Spectrometry (IRMS), is not adapted for in-situ continuous measurements of water vapor isotopes, the recent development of laser spectrometers offers a comparably easy and robust method to conduct in-the-field research with good time resolution. However, until now, most optical instruments require relative high humidity levels with water concentrations of at least several 1000 ppmv, which excludes measurements in some of the most interesting regions for water isotope research, such as the upper atmosphere and the central regions of Antarctica.In this work, we present a novel infrared laser spectrometer based on the technique OFCEAS, specifically designed to measure the four isotopologues H2_16O, H2_18O, H2_17O and HDO under very dry conditions, at water concentrations of some hundred to only tens of ppmv. The instrument developed during this thesis shows much higher measurement stability over time compared to previous OFCEAS instruments with optimum integration times of up to several hours and a very long effective path length of more than 30 km. At water concentrations around 80 ppmv, a precision of 0.8‰, 0.1‰ and 0.2‰ for d2H, d18O and d17O respectively could be achieved with an integration time of 30 to 60 min and at the optimum water concentration of ~650 ppmv, of 0.28‰, 0.02‰ and 0.07‰ respectively.An investigation of the overall performance of the instrument is presented and we specifically discuss the problem of a dependence of the isotope measurements on the water concentration at which a measurement is carried out. As main source of the concentration dependence, pattern noise is identified and a detailed analysis of the noise sources is given.Furthermore, a new calibration system for water vapor isotope measurements, the Syringe Nanoliter Injection Calibration System (SNICS), is introduced, which was developed in the framework of this thesis to offer a more reliable and stable means for the calibration of water vapor isotope measurements. This calibration system is based on the continuous injection of water into an evaporation chamber with two nanoliter syringe pumps and is able to generate standard water vapor in a range of 5 to 15 000 ppmv. A model simulation of the water injection is presented and shows a good agreement with experimental results.Subsequently, a first employment of the OFCEAS spectrometer at the Norwegian research station of Troll in Antarctica is discussed. Data from a three-week period from February and March 2011, during which the spectrometer continuously measured water vapor isotopologues in the atmosphere at the research station, is shown and problems and possibilities are discussed.Finally, the Isocloud project, an international project to study (super)saturation effects at the AIDA cloud chamber of the Karlsruhe Institute Technology in Germany, is introduced, in which we participated with both the spectrometer and the calibration instrument. Experimental data of the four measurement campaigns is presented, preliminary results are discussed. We conclude with a discussion of the optimum measurement protocol and give an outlook for the future.

abstract: This thesis describes the studies for two groups of molecules in the gas-phase: (a) copper monofluoride (CuF) and copper hydroxide (CuOH); (b) thorium monoxide (ThO) and tungsten carbide (WC). Copper-containing molecules (Group a) are selected to investigate the ionic bonding in transition metal-containing molecules because they have a relatively simple electronic state distribution due to the nearly filled 3d-orbital. ThO and WC (Group b) are in support of particle physics for the determination of electron electric dipole moment (eEDM), de, the existence of which indicates new physics beyond the Standard Model. The determination of the tiny eEDM requires large electric fields applied to the electron. The 3(Delta)1 states for heavy polar molecules were proposed [E. R. Meyer, J. L. Bohn, and M. P. Deskevich, Phys. Rev. A 73, 062108 (2006)] to determine de with the following attractive features: (1) large electric dipole moments; (2) large internal electric fields, Eeff, experienced by valence electrons; (3) nearly degenerate omega-doublets; (4) extremely small magnetic dipole moments. The H3(Delta)1 state for ThO and the X3(Delta)1 state for WC are both good candidates. Spectroscopic parameters (i.e. molecular electric and magnetic dipole moments, omega-doubling parameters, etc) are required for the 3(Delta)1 states of ThO and WC. High resolution optical spectra (linewidth ~50 MHz) of CuF, CuOH, ThO and WC were recorded field-free and in the presence of a static electric field (or magnetic field) using laser ablation source/supersonic expansion and laser induced fluorescence (LIF) detection. The spectra were modeled by a zero-field effective Hamiltonian operator and a Stark (or Zeeman) Hamiltonian operator with various molecular parameters. The determined molecular parameters are compared to theoretical predictions. The small omega-doubling parameter was well determined using the pump/probe microwave optical double resonance (PPMODR) technique with a much higher resolution (linewidth ~60 kHz) than optical spectroscopy. In addition to the above mentioned studies of the two groups of molecules, a resonance enhanced multi-photon ionization (REMPI) combined with a time-of-flight mass spectrometer (TOFMS) has been developed to identify the molecules responsible for observed LIF signals. The operation of this spectrometer has been tested by recording the mass spectrum of Ti/O2 and the REMPI spectrum for TiO using a two-color excitation scheme. / Dissertation/Thesis / Ph.D. Chemistry 2012