During this PhD thesis, cobalt (Co) catalysts have been prepared, characterized and studied in the carbon monoxide hydrogenation (CO+H2) reaction (also known as “Fischer-Tropsch” (FT) reaction). In industry, the FT synthesis aims at producing long chain hydrocarbons such as gasoline or diesel fuels. The interest is that the reactants (CO and H2) are obtained from other carbonaceous sources than crude oil: natural gas, coal, biomass or even petroleum residues. As it is well known that the worldwide crude oil reserves will be depleted in a few decades, the FT reaction represents an attractive alternative for the production of various fuels. Moreover, this reaction can also be used to produce high value specialty chemicals (long chain alcohols, light olefins…). Two different types of catalysts have been investigated during this thesis: cobalt with magnesia used as support or dispersant (Co/MgO) and cobalt with silica used as support (Co/SiO2). Each catalyst from the first class is prepared by precipitation of a mixed Co/Mg oxalate in acetone. This coprecipitation is followed by a thermal decomposition under reductive atmosphere leading to a mixed Co/MgO catalyst. On the other hand, Co/SiO2 catalysts are prepared by impregnation of a commercial silica support with a chloroform solution containing Co nanoparticles. This impregnation is then followed by a thermal activation under reductive atmosphere. The mixed Co/Mg oxalates and the resulting Co/MgO catalysts have been extensively characterized in order to gain a better understanding of the composition, the structure and the morphology of these materials: thermal treatments under reductive and inert atmospheres (followed by MS, DRIFTS, TGA and DTA), BET surface area measurements, XRD and electron microscopy studies have been performed. Moreover, an original in situ technique for measuring the H2 chemisorption surface area of catalysts has been developed and used over our catalysts. The performances of the Co/MgO and Co/SiO2 catalysts have then been evaluated in the CO+H2 reaction at atmospheric pressure. Chemical Transient Kinetics (CTK) experiments have been carried out in order to obtain information about the reaction kinetics and mechanism and the nature of the catalyst active surface under reaction conditions. The influence of several experimental parameters (temperature, H2 and CO partial pressures, total volumetric flow rate) and the effect of passivation are also discussed with regard to the catalyst behavior. Our results indicate that the FT active surface of Co/MgO 10/1 (molar ratio) is entirely covered by carbon, oxygen and hydrogen atoms, most probably associated as surface complexes (possibly formate species). Thus, this active surface does not present the properties of a metallic Co surface (this has been proved by performing original experiments consisting in switching from the CO+H2 reaction to the propane hydrogenolysis reaction (C3H8+H2) which is sensitive to the metallic nature of the catalyst). CTK experiments have also shown that gaseous CO is the monomer responsible for chain lengthening in the FT reaction (and not any CHx surface intermediates as commonly believed). Moreover, CO chemisorption has been found to be irreversible under reaction conditions. The CTK results obtained over Co/SiO2 are quite different and do not permit to draw sharp conclusions concerning the FT reaction mechanism. More detailed studies would have to be carried out over these samples. Finally, Co/MgO catalysts have also been studied on a combined DRIFTS/MS experimental set-up in Belfast. CTK and Steady-State Isotopic Transient Kinetic Analysis (SSITKA) experiments have been carried out. While formate and methylene (CH2) groups have been detected by DRIFTS during the FT reaction, the results indicate that these species play no role as active intermediates. These formates are most probably located on MgO or at the Co/MgO interface, while methylene groups stand for skeleton CH2 in either hydrocarbon or carboxylate. Unfortunately, formate/methylene species have not been detected by DRIFTS over pure Co catalyst without MgO, because of the full signal absorption.

This thesis presents the work involving two broad aspectswithin the field of nuclear reactor analysis and safety. Theseare: - development of a fully independent reactor dynamics andsafety analysis methodology of the RBMK-1500 core transientaccidents and - experiments on the enhancement of coolabilityof a particulate bed or a melt pool due to heat removal throughthe control rod guide tubes. The first part of the thesis focuses on the development ofthe RBMK-1500 analysis methodology based on the CORETRAN codepackage. The second part investigates the issue of coolabilityduring severe accidents in LWR type reactors: the coolabilityof debris bed and melt pool for in- vessel and ex-vesselconditions. The safety of the RBMK type reactors became an importantarea of research after the Chernobyl accident. Since 1989,efforts to adopt Western codes for the RBMK analysis and safetyassessment are being made. The first chapters of this Thesisdescribe the development of an independent neutron dynamics andsafety analysis methodology for the RBMK-1500 core transientsand accidents. This methodology is based on the codes HELIOSand CORETRAN. The RBMK-1500 neutron cross section library wasgenerated with the HELIOS code. The ARROTTA part of theCORETRAN code performs three dimensional neutron dynamicsanalysis and the VIPRE-02 part of the CORETRAN package performsthe rod bundle thermal hydraulics analysis. The VIPRE-02 codewas supplemented with additional CHF correlations, used inRBMK-type reactor calcula tions. The validation, verificationand assessment of the CORETRAN code model for RBMK-1500 wereperformed and are described in the thesis. The second part of the thesis describes the in- vesselparticulate debris bed and melt pool coolabilityinvestigations. The role of the control rod guide tubes (CRGTs)in enhancing the coolability during a postulated severeaccident in a BWR was investigated experimentally. Thisinvestigation is directed towards the accident managementscheme of retaining the core melt within the BWR lowerhead. The particulate debris bed coolability was also investigatedduring the ex-vessel severe accident situation, having a flowof non-condensable gases through the porous debris bed.Experimental investigations on the dependence of the quenchingtime on the non-condensable gas flow rate were carriedout. The first chapter briefly presents the status ofdevelopments in both the RBMK- 1500 core analysis and thecorium coolability areas. The second chapter describes the generation of the RBMK-1500neutron cross section data library with the HELIOS code. Thecross section library was developed for the whole range of thereactor conditions (i.e. for both cold and hot reactor states).The results of the benchmarking with the WIMS-D4 code andvalidation against the RBMK Critical Facility experiments isalso presented here. The HELIOS generated neutron cross sectiondata library provides a close agreement with the WIMS-D4 coderesults. The validation against the data from the CriticalExperiments shows that the HELIOS generated neutron crosssection library provides excellent predictions for thecriticality, axial and radial power distribution, control rodreactivity worths and coolant reactivity effects, etc. Thereactivity effects of voiding for the system, fuel assembly andadditional absorber channel are underpredicted in thecalculations using the HELIOS code generated neutron crosssections. The underprediction, however, is much less than thatobtained when the WIMS-D4 code generated cross sections areemployed. The third chapter describes the work, performed towards theaccurate prediction, assessment and validation of the CHF andpost-CHF heat transfer for the RBMK- 1500 reactor fuelassemblies employing the VIPRE-02 code. This chapter describesthe experiments, which were used for validating the CHFcorrelations, appropriate for the RBMK-1500 type reactors.These correlations after validation were added to the standardversion of the VIPRE-02 code. The VIPRE-02 calculations werebenchmarked against the RELAP5/MOD3.3 code. It was found thatthese user-coded additional CHF correlations developed for theRBMK type reactors (Osmachkin, RRC KI and Khabenskicorrelations) and implemented into the code by the author,provide a good prediction of the CHF occurrence at the RBMKreactor nominal pressure range (at about 7 MPa). Transition andfilm boiling are also predicted well with the VIPRE-02 code forthis pressure range. It was found, that for the RBMK- 1500reactor applications, EPRI CHF correlation should be used forthe CHF predictions for the lower fuel assemblies of thereactor in the subchannel model of the RBMK-1500 fuel assembly.RRC KI and Bowring CHF correlations may be used for the upperfuel assemblies. For a single-channel model of the RBMK-1500fuel channel, Osmachkin, RRC KI and Bowring correlationsprovide the closest predictions and may be used for the CHFestimation. For the low coolant mass fluxes in the fuelchannel, Khabenski correlation can be applied. The fourth chapter presents the verification of the CORETRANcode for the RBMK-1500 core analysis (HELIOS generated neutroncross section data, coupled CORETRAN 3-D neutron kineticscalculations and VIPRE-02 thermal hydraulic module). The modelwas verified against a number of RBMK-1500 plant data andtransient calculations. The new RBMK-1500 core model wassuccessfully applied in several safety assessment applications.A series of transient calculations, considered within the scopeof the RBMK-type reactor Safety Analysis Report (SAR), wereperformed. Several cases of the transient calculations arepresented in this chapter. The HELIOS/CORETRAN/VIPRE-02 coremodel for the RBMK-1500 is fully functional. The RBMK-1500 CPSlogic, added into the CORETRAN provides an adequate response tothe changes in the reactor parameters. Chapters 5 and 6 describe the experiments and the analysisperformed on the coolability of particulate debris bed and meltpool during a postulated severe accident in the LWR. In theChapter 5, the coolability potential, offered by the presenceof a large number of the Control Rod Guide Tubes (CRGTs) in theBWR lower head is presented. The experimental investigationsfor the enhancement of coolability possible with CRGTs wereperformed on two experimental facilities: POMECO (POrous MEdiumCOolability) and COMECO (COrium MElt COolability). Theinfluence of the coolant supply through the CRGT on the debrisbed dryout heat flux, debris bed and melt pool quenching time,crust growth rate, etc. were examined. The heat removalcapacity offered by the presence of the CRGT was quantifiedwith the experimental data, obtained from the POMECO and COMECOfacilities. It was found that the presence of the CRGTs in thelower head of a BWR offers a substantial potential for heatremoval during a postulated severe accident. Additional 10-20kW of heat were removed from the POMECO and COMECO testsections through the CRGT. This corresponds to the average heatflux on the CRGT wall equal to 100-300 kW/m2. In the Chapter 6 the ex-vessel particulate debris bedcoolability is investigated, considering the non-condensablegases released from the concrete ablation process. Theinfluence of the flow of the non-condensable gases on theprocess of quenching a hot porous debris bed was considered.The POMECO test facility was modified, adding the air supply atthe bottom of the test section, to simulate the noncondensablegas release. The process was investigated for both high and lowporosity debris beds. It was found that for the low porositybed composition the countercurrent flooding limit could beexceeded, which would degrade the quenching process for suchbed compositions. The experimental results were analyzed withseveral CCFL models, available in the literature. Keywords:RBMK, light water reactor, core analysis,transient analysis, reactor dynamics, RIA, ATWS, critical heatflux, post-CHF, severe accidents, particulate debris beds, meltpool coolability, BWR, CRGT, dryout, quenching, CCFL, crustgrowth, solidification, water ingression, heat transfer.

Due to the low current ratings of the currently available silicon carbide (SiC) switches they cannot be employed in high-power converters. Thus, it is necessary to parallel-connect several switches in order to reach higher current ratings. This paper presents an investigation of parallel-connected normally-on SiC junction field effect transistors. There are four crucial parameters affecting the effectiveness of the parallel-connected switches. However, the pinch-off voltage and the reverse breakdown voltage of the gates seem to be the most important parameters which affect the switching performance of the devices. In particular, the spread in these two parameters might affect the stable off-state operation of the switches. The switching performance and the switching losses of a pair of parallel-connected devices having different reverse breakdown voltages of the gates is investigated by employing three different gate-driver configurations. It is experimentally shown that using a single gate-driver circuit the switching performance of the parallel-connected devices is almost identical, while the total switching losses are lower compared to the other two configurations. / <p>QC 20121116</p>

Small wind turbine installations have a variety of potential uses, each with unique performance demands and operating conditions. Many applications require that the turbine is placed in wind conditions that are not ideal for optimum operation. Better predictive techniques can improve wind turbine performance through improved control strategies and enhanced designs. Conventional methods of wind power design and control utilize an average power coefficient. In this thesis, various techniques to predict the transient power coefficient of a wind turbine are developed. The operation of a Savonius wind turbine is accurately represented, with a new model which considers the flow distributions to predict the changes in power output at all rotor positions. Another model is developed that represents the dynamics of a small horizontal wind turbine, including the effect of transient wind conditions on rotor speed and acceleration. These can supplement current methods to determine turbine placement, selection and categorization.

To support the increasingly demanding requirements for power conversion units, a digitally controlled dual output stage buck converter is designed. The system consists of a dual output stage, which includes an auxiliary buck output stage connected in parallel with a main output stage. The auxiliary output stage is only active during load transient to suppress the output voltage variation. A digital controller is designed to control both stages with a linear/nonlinear control scheme. Nonlinear control is applied during load transient based on the capacitor charge balance principle; whereas linear PID control governs the steady state operation. The design is verified with simulation and experimentally with discrete components. The controller is realized with a FPGA with preset output stage parameters. The experimental result shows a 60% reduction of output voltage variation for a heavy-to-light load transient.

The research conducted in this thesis provides a robust implementation of a preconditioned iterative linear solver on programmable graphic processing units (GPUs). Solving a large, sparse linear system is the most computationally demanding part of many widely used power system analysis. This thesis presents a detailed study of iterative linear solvers with a focus on Krylov-based methods. Since the ill-conditioned nature of power system matrices typically requires substantial preconditioning to ensure robustness of Krylov-based methods, a polynomial preconditioning technique is also studied in this thesis. Implementation of the Chebyshev polynomial preconditioner and biconjugate gradient solver on a programmable GPU are presented and discussed in detail. Evaluation of the performance of the GPU-based preconditioner and linear solver on a variety of sparse matrices shows significant computational savings relative to a CPU-based implementation of the same preconditioner and commonly used direct methods.

To support the increasingly demanding requirements for power conversion units, a digitally controlled dual output stage buck converter is designed. The system consists of a dual output stage, which includes an auxiliary buck output stage connected in parallel with a main output stage. The auxiliary output stage is only active during load transient to suppress the output voltage variation. A digital controller is designed to control both stages with a linear/nonlinear control scheme. Nonlinear control is applied during load transient based on the capacitor charge balance principle; whereas linear PID control governs the steady state operation. The design is verified with simulation and experimentally with discrete components. The controller is realized with a FPGA with preset output stage parameters. The experimental result shows a 60% reduction of output voltage variation for a heavy-to-light load transient.

The research conducted in this thesis provides a robust implementation of a preconditioned iterative linear solver on programmable graphic processing units (GPUs). Solving a large, sparse linear system is the most computationally demanding part of many widely used power system analysis. This thesis presents a detailed study of iterative linear solvers with a focus on Krylov-based methods. Since the ill-conditioned nature of power system matrices typically requires substantial preconditioning to ensure robustness of Krylov-based methods, a polynomial preconditioning technique is also studied in this thesis. Implementation of the Chebyshev polynomial preconditioner and biconjugate gradient solver on a programmable GPU are presented and discussed in detail. Evaluation of the performance of the GPU-based preconditioner and linear solver on a variety of sparse matrices shows significant computational savings relative to a CPU-based implementation of the same preconditioner and commonly used direct methods.

Cellular/subcellular imaging of biological tissue is an important tool for understanding disease mechanisms. Many current techniques for subcellular absorption contrast imaging, such as two-photon excited fluorescence (TPEF), require exogenous contrast agents to gain access to many naturally occurring biomolecules. Non-fluorescent biomolecules must have a fluorescent marker (tag) chemically bound in order to be observed by TPEF. Contrast agents and markers, while effective, are not an optimal solution because they can change the local environment in the biological system and require FDA approval for human use. Photoacoustic microscopy (PAM) is an imaging modality with high endogenous absorption contrast and penetration depth due to its ability to detect acoustic waves, which are attenuated much less than light in tissue. However, this technique suffers from poor axial resolution, precluding it from consideration for subcellular imaging. This manuscript describes the author's efforts to improve the axial resolution of traditional PAM by merging it with pump-probe spectroscopy. Pump-probe spectroscopy is a non-linear optical technique that exploits a physical process called transient absorption, providing spatial resolution equivalent to two-photon microscopy and access to molecular-specific traits, such as the ground state recovery time and transient absorption spectrum. These traits provide molecular contrast to the imaging technique, which is highly desirable in a complex, multi-chromophore biological system. In this manuscript, a novel technique called transient absorption ultrasonic microscopy (TAUM) is designed and characterized in detail. A second-generation TAUM system is also described, which improves speed and sensitivity of TAUM by up to 1000-fold. This system is validated by collecting volumes of red blood cells in blood smears and tissue samples. These results constitute the first time single cells have been fully resolved using a photoacoustic microscope. Finally, the TAUM system is modified to measure chromophore ground state recovery times. This technique is validated by measuring the recovery time of Rhodamine 6G, which matches well with published values of the fluorescence lifetime. Recovery times of oxidized and reduced forms of hemoglobin are also measured and shown to statistically differ from one another, suggesting the possibility of subcellular measurements of oxygen saturation in future iterations of TAUM.

Numerical relays are the result of the application of microprocessor technology in relay industry. Numerical relays have the ability to communicate with its peers, are economical and are easy to operate, adjust and repair. Modeling of digital and numerical relays is important to adjust and settle protection equipment in electrical facilities and to train protection personnel. Designing of numerical relays is employed to produce new prototypes and protection algorithms. Computer models of numerical relays for the study of protection systems are greatly enhanced when working along with an electromagnetic transient program (emtp). A literature survey has revealed that previous modeling techniques presented a lack of automation in the generation of relay models, or show high complexity in linking the numerical relay models with the power system modeled in the emtp. <p> This thesis describes a new approach of modeling and designing of numerical relays. The proposed methodology employs a Visual C++-based program (PLSA) to obtain from the user the specifications of the relay to be designed, and to process this information to generate the FORTRAN code that represents the functional blocks of the relay. This generated code is incorporated in a PSCAD/EMTDC case using a resource called component, which facilitates the creation of user-custom models in PSCAD/EMTDC. Convenient electrical and logical signals are connected to the inputs and outputs of the PSCAD/EMTDC component. Further additions of digital relay models into the PSCAD/EMTDC case constitute the protection system model. The thesis describes a procedure for designing distance and differential relay models, but the methodology may be extended to design models of other relay elements. <p> A number of protection system studies were performed with the structure created with the proposed methodology. Adjustment of distance and differential relays were studied. Relay performance under CT saturation and the effects of the removal of anti-aliasing analog filter were investigated. Local and remote backup distance protection of transmission lines was simulated. The adjustment of differential protection of power transformer to overcome the effects of inrush current was performed. Power transformer differential protection responses to internal and external faults were considered. <p>Additionally, a set of tests were performed to investigate the consistency of the relay models generated with the proposed methodology. The results showed that the numerical relay models respond satisfactorily according with the expected results of the tests.