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

This master's thesis covers an investigation of the reduction behavior of different iron oxides when electrolytically reduced with molten salt electrolysis (MSE). The tested iron oxides were wüstite (FeO), hematite (Fe2O3), magnetite (Fe3O4) and magnetite ore concentrate from the Tapuli deposit in Pajala, Norrbotten, Sweden. The properties of the Tapuli magnetite ore and magnetite ore concentrate were analysed from a mineralogical perspective to evaluate how the raw ore material influences the concentrate and its reduction by the MSE technology. The electrolytic experiments were performed in an Inconel 625 cell body within a pit-furnace. The different iron oxides were tested separately. The reduction samples were constructed of one or three iron oxide briquettes of 20 g each within a molybdenum mesh attached on a molybdenum tray with molybdenum wires. The molten electrolyte was kept at 500°C with an applied voltage of 1.7 or 2.1 V. The used electrolyte was sodium hydroxide (NaOH). The mineralogical examination shows that the Tapuli ore varies in composition between different locations of the deposit with respect to magnetite grain size and skarn composition and grain size. Point analyses with Laser Ablation Single Collector Inductively Coupled Plasma Mass Spectrometry (LA-SC-ICP-MS) on magnetite grains in thin sections from five drill cores fromdifferent parts of the deposit show that the element composition in the magnetite grains vary between the samples. Core-to-rim analyses for Fe, Mg, Mn and Al reveal relatively homogenous grades throughout the grains, with a few exceptions. Phase analysis with XRD shows that reduction has occurred in all tested iron oxides. Without prevention, the reduction products from trials on Fe2O3, Fe3O4 and magnetite ore concentrate show distinct XRD peaks of the by-product NaFeO2. According to XRD, the addition of Na2O seems to have reduced the NaFeO2 formation. Interestingly, no NaFeO2 was formed in the FeO trials. This might be explained by the absence of Fe3+ in FeO. The variation of the current-time curves of the trials is interpreted to depend on the voltage applied, the number of briquettes, briquette decomposition and Na2O addition. Electrolysis in molten NaOH can be used to reduce iron oxides. Despite this, NaOH might not be a suitable electrolyte for this process due to its interaction with Fe2O3 and Fe3O4 resulting information of NaFeO2. Na2O can be used as an additive to prevent formation of NaFeO2 but sharply decreases the current response, thus having an apparent negative effect on the process efficiency. Another preventive measure that can be tested is to calibrate the process voltage to decompose the NaFeO2 but not NaOH. Due to the shown interaction tendency of NaOH, other electrolytes should however be considered for this process. Regarding the Tapuli ore concentrate, more tests are needed to draw conclusions about how the trace elements effects its electrolytic behavior. / Denna masteruppsats avhandlar en undersökning av reduktionsbeteendet hos olika järnoxider vid elektrolytisk reduktion i saltsmälta (molten salt electrolysis (MSE)). Järnoxiderna som har testats är wüstit (FeO), hematit (Fe2O3), magnetit (Fe3O4) och magnetitmalmkoncentrat från malmfyndigheten Tapuli i Pajala, Norrbotten, Sverige. Malmkoncentratets egenskaper har analyserats ur mineralogisk synvinkel för att utvärdera hur den råa malmens mineralogi påverkar koncentratet och dess reduktionsbeteende vid elektrolys i saltsmälta. Elektrolysexperimenten utfördes i cellkropp av Inconel 625 placerad i en gropugn. De olika järnoxiderna testades separat. Reduktionsproverna utgjordes av en eller tre järnoxidbriketter på 20 g inuti ett molybdennät, fastvirade på en molybdenbricka med molybdentråd. Den smälta elektrolyten hölls vid en temperatur av 500°C med en applicerad spänning av 1.7 eller 2.1 V. Elektrolyten som användes var natriumhydroxid (NaOH). Den mineralogiska undersökningen visar att tapulimalmens sammansättning varierar mellan olika delar av fyndigheten med avseende på magnetitens kornstorlek och skarnets sammansättning och kornstorlek. Punktanalyser med Laser Ablation Single Collector Inductively Coupled Plasma Mass Spectrometry (LA-SC-ICP-MS) på magnetitkorn i tunnslip från fem olika borrkärnor visar att elementkoncentrationerna i magnetitkornen varierar mellan proverna. Core-to-rim-analyser på magnetitkornen visar att halterna av Fe, Mg, Mn och Al är tämligen homogena genom hela magnetitkornet med undantag av några få avvikande punkter. Fasanalys med XRD indikerar att reduktion har skett i alla försök. Utan prevention visar reduktionsprodukterna från försöken på Fe2O3, Fe3O4 och magnetitmalmkoncentrat klara indikationer av biprodukten NaFeO2. Enligt XRD verkar tillsats av Na2O ha minskat bildningen av Na2O för Fe2O3, Fe3O4 och Tapuli magnetitmalmkoncentrat. Intressant är att ingen NaFeO2 bildades i försöken med FeO. Förklaringen till detta skulle kunna vara avsaknaden av Fe3+ i FeO. De varierande ström-tidkurvorna från försöken tolkas bero på den applicerade spänningen, antalet briketter, brikettsönderdelning och tillsats av Na2O. Elektrolys i smält NaOH kan användas för att reducera järnoxider. Trots detta kanske NaOH inte är lämplig som elektrolyt i denna process, detta på grund av dess påvisade interaktion med Fe2O3 och Fe3O4 som resulterar i bildning av NaFeO2. Na2O kan tillsättas för att förhindra bildning av NaFeO2 men har en kraftigt negativ effekt på strömstyrkan i processen vilket minskar processens effektivitet. En annan preventiv åtgärd som kan testas är att kalibrera processens spänning så att NaFeO2 sönderdelas men inte NaOH. På grund av den konstaterade interaktionstendensen hos NaOH bör andra elektrolyter tas i beaktande för denna process. Angående magnetitmalmskoncentratet från Tapuli behövs fler tester för att dra slutsatser kring hur spårelementen påverkar dess uppförande vid smältelektrolys.

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