Rare earth and actinide metals, critical to security, medicine, and the economy, have been processed through methods such as solvent extraction and electrorefining. To minimize radiological waste and improve yield, a 'chloride volatility' process--also known as the chlorination and volatilization process (CVP)--has been proposed and demonstrated for processing rare earths. The process takes advantage of the low vapor pressure of rare earth chlorides (<700 >°C), CaCl2 was added to LaCl3 to lower the melting temperature. LaCl3 electrochemical behavior has not previously been studied in CaCl2. Cyclic voltammetry (CV) and square wave voltammetry (SWV) were applied to LaCl3 salts in CaCl2-LiCl and CaCl2 to study the metal ion behavior. Various electrode materials were compared at low CV scan rates (s-1) to determine compatibility with chlorine gas evolution. Experiments of eutectic LaCl3-CaCl2 were performed and analyzed to determine the efficacy of chlorine gas generation via electrolysis for the CVP. Through galvanostatic electrolysis, oxidation of chloride ions and subsequent chlorination of rare earth was demonstrated, with cerium chosen as the representative rare earth metal. Through a quadrupole mass spectrometer plumbed in line with the electrolytic cell, the quality of the generated gas was analyzed.

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Over the last two decades, there has been widespread international interest in the development of the molten salt reactor concept due to its passive safety, high coolant boiling temperature, low operational pressure, high thermal efficiency, and ease of breeding. Terrestrial Energy Incorporated (TEI) is developing a thermal-spectrum converter type molten salt reactor, called the Integral Molten Salt Reactor (IMSR-400) to be built by 2030. A physics experiment is needed in order to validate the theoretical predictions of the temperature reactivity coefficients of the IMSR-400. This thesis will determine the feasibility of conducting a subcritical experiment, utilizing a Deuterium-Deuterium Fusion Neutron Source (DD). / Thesis / Master of Science (MSc)

A breed-and-burn molten salt reactor (BBMSR) concept is proposed to address the Generation IV fuel cycle sustainability objective in a once-through cycle with low enrichment and no reprocessing. The BBMSR uses separate fuel and coolant molten salts, with the fuel contained in assemblies of individual tubes that can be shuffled and reclad periodically to enable high burnup. In this dual-salt configuration, the BBMSR may overcome several limitations of previous breed-and-burn (B$\&$B) designs to achieve high uranium utilisation with a simple, passively safe design. A central challenge in design of the BBMSR fuel is balancing the neutronic requirement of large fuel volume fraction for B$\&$B mode with the thermal-hydraulic requirements for safe and economically competitive reactor operation. Natural convection of liquid fuel within the tubes aids heat transfer to the coolant, and a systematic approach is developed to efficiently model this complex effect. Computational fluid dynamics modelling is performed to characterise the unique physics of the system and produce a new heat transfer correlation, which is used alongside established correlations in a numerical model. A design framework is built around this numerical model to iteratively search for the limiting power density of a given fuel and channel geometry, applying several defined temperature and operational constraints. It is found that the trade-offs between power density, core pressure drop, and pumping power are lessened by directing the flow of coolant downwards through the channel. Fuel configurations that satisfy both neutronic and thermal-hydraulic objectives are identified for natural, 5$\%$ enriched, and 20$\%$ enriched uranium feed fuel. B$\&$B operation is achievable in the natural and 5$\%$ enriched versions, with power densities of 73 W/cm$^3$ and 86 W/cm$^3$, and theoretical uranium utilisations of 300 $\mathrm{MWd/kgU_{NAT}}$ and 25.5 $\mathrm{MWd/kgU_{NAT}}$, respectively. Using 20$\%$ enriched feed fuel relaxes neutronic constraints so a wider range of fuel configurations can be considered, but there is a strong inverse correlation between power density and uranium utilisation. The fuel design study demonstrates the flexibility of the BBMSR concept to operate along a spectrum of modes ranging from high fuel utilisation at moderate power density using natural uranium feed fuel, to high power density and moderate utilisation using 20$\%$ uranium enrichment.

Transition-metal chemistry in ionic liquids (IL) has achieved intrinsic fascination in the last few years. The use of an IL as environmental friendly solvent, offers many advantages over traditional materials synthesis methods. The change from molecular to ionic reaction media leads to new types of materials being accessible. Room-temperature IL have been found to be excellent media for stabilising transition-metal clusters in solution and to crystallise homo- and heteronuclear transition-metal complexes and clusters. Furthermore, the use of IL as solvent provides the option to replace high-temperature routes, such as crystallisation from the melt or gas-phase deposition, by convenient room- or low-temperature syntheses. Inorganic IL composed of alkali metal cations and polynuclear transition-metal cluster anions are also known. Each of these areas will be discussed briefly in this contribution. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

High dielectric constant materials are of technological importance as they lead to the miniaturization of the electronic devices. For instance, in the case of memory devices based on capacitive components, such as static and dynamic random access memories, the dielectric constant will ultimately decide the level of miniaturization. In this context, the observation of anomalously high dielectric constant (>10) in the double perovskite Sr2SbMnO6 (SSM) over wide frequency (100 Hz1 MHz) and (190373 K) temperature range has attracted a great deal of attention. However, unfortunately their dielectric losses were also high which limit their use for possible capacitor and related applications. The dielectric loss however was known to decrease with decreasing crystallite size in electroceramics. Therefore, the present work has been focused on the synthesis of nanocrystalline SSM powders by moltensalt route. The characterization of the ceramics fabricated from these powders for their microstructural and dielectric properties. A cubic phase of SSM powder was obtained by calcining the as synthesized powders at 900°C/10h by using sulphate flux. The crystallite size was ~ 60 nm. The activation energy associated with the particle growth was found to be 95 ± 5 kJmol-1 . The ceramic sintered at 1075°C/16h exhibited high dielectric constant (>10at 1 kHz) with low loss (0.72 at 1 kHz) at room temperature. The results are interpreted in terms of a twolayer model with conducting grains partitioned from each other by poorly conducting grain boundaries. Using this model, we attributed the two electrical responses in impedance and modulus formalisms to the grain and grain boundary effects, respectively, while the detected Debyelike relaxation and large dielectric constant were explained in terms of MaxwellWagner relaxation.

Cette thèse s'intéresse à la coordination des sous-systèmes d'un nouveau genre de centrale de production d'énergie : un cycle combiné hybride (HCC - Hybrid Combined Cycle). Cette centrale HCC n'existe pas encore mais combine un cycle combiné gaz (CCG), un moyen de production solaire thermodynamique (miroirs cylindro-paraboliques) et un moyen de stockage thermique (stockage indirect de chaleur sensible utilisant deux réservoirs de sels fondus). Comment coordonner ces trois sous-systèmes de manière optimale lors des variations de demande de puissance ou des prix du gaz ?Dans un premier temps, chacun des trois sous-systèmes est étudié de manière indépendante afin d'obtenir, d'une part, un modèle physique permettant de caractériser le comportement dynamique du sous-système considéré et, d'autre part, un contrôle local qui agit en fonction des objectifs de fonctionnement prédéfinis. Un modèle du système complet interconnecté de l'HCC est ensuite obtenu en couplant les modèles des trois sous-systèmes. Enfin, une coordination des différents sous-systèmes est mise en place pour adapter le fonctionnement de chacun, en fonction des objectifs globaux de la centrale HCC complète, en optimisant les consignes de chaque sous-système. Dans ce travail, une coordination de type linéaire quadratique et une coordination de type optimale prédictive sont étudiées. Les résultats obtenus sont bien prometteurs : ils montrent, tout d'abord, que lors d'un appel de puissance, la commande coordonnée permet au système HCC de répondre plus rapidement, en utilisant plus efficacement la partie solaire. De plus, lorsque la demande subit beaucoup de variations, la partie solaire et la partie stockage absorbent toutes ces variations et la Turbine à Combustion (TAC) du CCG est beaucoup moins sollicitée. Lorsqu'il n'y a plus d'irradiation solaire, la partie stockage prend la relève pour continuer à produire de la vapeur solaire, jusqu'à ce que les stocks se vident. Finalement, le stockage permet d'ajuster la production de la TAC en fonction des prix du gaz. / This work concerns the subsystems coordination of a new type of power plant: a Hybrid Combined Cycle (HCC). This HCC plant is not yet build but consists of a Combined Cycle Power Plant (CCPP), a concentrated solar plant (parabolic trough) and a thermal storage system (a molten-salts two-tank indirect sensible thermal storage). How to coordinate these three subsystems optimally during variations in power demand or in gas price?First, each subsystem is studied independently in order to get on one hand a physical model that reproduces the dynamical behavior of the considered subsystem, and on the other hand, a local control that achieves an operation according to pre-specified objectives. Then, a model of the HCC system is obtained by coupling the models of the three defined subsystems.Eventually, a coordination of the subsystems is set up in order to adapt the behavior of each subsystem according to the global objectives for the full HCC system, by optimizing subsystem setpoints. In this study, a linear quadratic coordination and a model predictive coordination are designed. The obtained results are promising: they first show that during a power demand, the coordination allows the global system to quickly respond, using extensively the solar production. Besides, when the power demand undergoes many fluctuations, the solar and storage parts absorb these variations and the gas turbine of the CCPP is much less stressed. In addition, when there is no more solar radiation, the storage part continues producing solar steam, until storage tanks are empty. At last, the storage part allows to adjust the gas turbine production according to the gas prices.

Transition-metal chemistry in ionic liquids (IL) has achieved intrinsic fascination in the last few years. The use of an IL as environmental friendly solvent, offers many advantages over traditional materials synthesis methods. The change from molecular to ionic reaction media leads to new types of materials being accessible. Room-temperature IL have been found to be excellent media for stabilising transition-metal clusters in solution and to crystallise homo- and heteronuclear transition-metal complexes and clusters. Furthermore, the use of IL as solvent provides the option to replace high-temperature routes, such as crystallisation from the melt or gas-phase deposition, by convenient room- or low-temperature syntheses. Inorganic IL composed of alkali metal cations and polynuclear transition-metal cluster anions are also known. Each of these areas will be discussed briefly in this contribution. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Um die Wirtschaftlichkeit von Solarkraftwerken zu verbessern, sollte geprüft werden, inwieweit eine geschmolzene Mischung aus Natriumchlorid und Aluminiumchlorid als Wärmetransportflüssigkeit in Frage kommt. Aufgrund der Hydrolyseempfindlichkeit solcher Schmelzen kommt es durch Einwirkung von Wasser zur Bildung von Chlorwasserstoff sowie Aluminiumoxidchloriden, die in einem geschlossenen System zu einem Druckanstieg bzw. Ausfällungen führen können. Der Gesamtdruck über schwach basischen NaCl-AlCl3-Schmelzen wird durch eine hohe HCl-Löslichkeit herabgesetzt, sodass aus der Bilanz heraus ein Hydrolysegrad von ca. 50 % angenommen werden kann. Für die wassermengenabhängige Verfolgung des Druckes diente eine statische Methode mit einem Drucksensor. Der Oxidgehalt wurde voltammetrisch durch Titration mit TaCl5 und die HCl-Löslichkeit durch eine Elutionsmethode ermittelt. Für Informationen zum Lösungszustand der Hydrolyseprodukte wurden 1H- und 27Al-NMR-Spektren von hydrolysierten Schmelzen aufgenommen.

This work focusses on analysing the stability of the MSFR – a molten salt reactor with a fast neutron spectrum. The investigations are based on a model, which was published and studied by the Politecnico di Milano using a linear approach. Since linear methods can only provide stability information to a limited extent, this work continues the conducted investigations by applying nonlinear methods. In order to examine the specified reactor model, the system equations were implemented, adjusted and verified using MATLAB code. With the help of the computational tool MatCont, a so-called fixed-point solution was tracked and its stability monitored during the variation of selected control parameters. It was found that the considered fixed point does not change its stability state and remains stable. Coexisting fixed points or periodic solutions could not be detected. Therefore, the analysed MSFR model is considered to be a stable system, in which the solutions always tend towards a steady state.:1. Introduction 2. Molten Salt Reactor Technology 2.1. Introduction 2.2. Historical Development 2.3. Working Principle of Molten Salt Reactors 2.4. Molten Salt Coolants 2.5. Advantages and Drawbacks 2.6. Classification 2.7. Molten Salt Fast Reactor Design 3. Stability Characteristics of Dynamical Systems 3.1. Introduction 3.2. Dynamical Systems 3.3. Stability Concepts 3.3.1. Introduction 3.3.2. Lagrange Stability (Bounded Stability) 3.3.3. Lyapunov Stability 3.3.4. Poincaré Stability (Orbital Stability) 3.4. Fixed-Point Solutions 3.4.1. Stability Analysis of Fixed-Point Solutions 3.4.2. Bifurcations of Fixed-Point Solutions 3.5. Periodic Solutions 3.5.1. Stability Analysis of Periodic Solutions 3.5.2. Bifurcations of Periodic Solutions 4. Analysed Reactor System 4.1. Introduction 4.2. Specified Reactor Model 4.3. Implementation and Verification of the Linearised System of Equations 4.3.1. Linearised System of Delayed Differential Equations 4.3.2. Comparison with Reference Plots 4.3.3. Adaptation of Parameter Values 4.4. Implementation and Verification of the Nonlinear System of Equations 4.4.1. Nonlinear System of Delayed Differential Equations 4.4.2. Delayed Neutron Precursor Equation Adjustments 4.4.3. Salt Temperature Equation Adjustments 4.4.4. Nonlinear System of Ordinary Differential Equations 4.4.5. Verification of the Nonlinear System of Ordinary Differential Equations 5. Conducted Stability Analyses 5.1. Introduction 5.2. Nonlinear Stability Analysis 5.2.1. Implementation 5.2.2. Results 5.2.3. Interpretation 5.3. Linear Stability Analysis 5.3.1. Comparison Between the Linearised and Nonlinearised MSFR System of Equations 5.3.2. Stability Investigations Using a Linear Criterion 5.4. MatCont Reliability Test Using an MSBR Model 6. Conclusions and Recommendations for Future Studies / Im Fokus dieser Arbeit steht die Stabilitätsanalyse des MSFR – eines Flüssigsalzreaktors mit schnellem Neutronenspektrum. Als Grundlage wurde ein Modell verwendet, das am Politecnico di Milano erstellt und dort mittels linearer Methoden untersucht wurde. Da lineare Betrachtungen nur eingeschränkte Stabilitätsaussagen treffen können, erweitert diese Arbeit die Untersuchungen um die nichtlineare Stabilitätsanalyse. Zur Untersuchung des vorgegebenen Reaktormodells wurden die Systemgleichungen in MATLAB übertragen und verifiziert. Mithilfe der Rechensoftware MatCont wurde eine sogenannten Fixpunkt-Lösung des Modells unter der Variation ausgewählter Parameter verfolgt und deren Stabilität überprüft. Es hat sich gezeigt, dass der betrachtete Fixpunkt seinen Stabilitätszustand dabei nicht verändert und stabil bleibt. Koexistierende Fixpunkte oder periodische Lösungen konnten nicht nachgewiesen werden. Daher gilt das betrachtete MSFR-Modell als ein stabiles System, dessen Lösungen immer auf einen stationären Zustand zulaufen.:1. Introduction 2. Molten Salt Reactor Technology 2.1. Introduction 2.2. Historical Development 2.3. Working Principle of Molten Salt Reactors 2.4. Molten Salt Coolants 2.5. Advantages and Drawbacks 2.6. Classification 2.7. Molten Salt Fast Reactor Design 3. Stability Characteristics of Dynamical Systems 3.1. Introduction 3.2. Dynamical Systems 3.3. Stability Concepts 3.3.1. Introduction 3.3.2. Lagrange Stability (Bounded Stability) 3.3.3. Lyapunov Stability 3.3.4. Poincaré Stability (Orbital Stability) 3.4. Fixed-Point Solutions 3.4.1. Stability Analysis of Fixed-Point Solutions 3.4.2. Bifurcations of Fixed-Point Solutions 3.5. Periodic Solutions 3.5.1. Stability Analysis of Periodic Solutions 3.5.2. Bifurcations of Periodic Solutions 4. Analysed Reactor System 4.1. Introduction 4.2. Specified Reactor Model 4.3. Implementation and Verification of the Linearised System of Equations 4.3.1. Linearised System of Delayed Differential Equations 4.3.2. Comparison with Reference Plots 4.3.3. Adaptation of Parameter Values 4.4. Implementation and Verification of the Nonlinear System of Equations 4.4.1. Nonlinear System of Delayed Differential Equations 4.4.2. Delayed Neutron Precursor Equation Adjustments 4.4.3. Salt Temperature Equation Adjustments 4.4.4. Nonlinear System of Ordinary Differential Equations 4.4.5. Verification of the Nonlinear System of Ordinary Differential Equations 5. Conducted Stability Analyses 5.1. Introduction 5.2. Nonlinear Stability Analysis 5.2.1. Implementation 5.2.2. Results 5.2.3. Interpretation 5.3. Linear Stability Analysis 5.3.1. Comparison Between the Linearised and Nonlinearised MSFR System of Equations 5.3.2. Stability Investigations Using a Linear Criterion 5.4. MatCont Reliability Test Using an MSBR Model 6. Conclusions and Recommendations for Future Studies