Fuel cells are promising candidates for converting chemical energy into electrical energy. The Molten Carbonate Fuel Cell (MCFC) is a high temperature fuel cell that produces electrical energy from a variety of fuels containing hydrogen, hydrocarbons and carbon monoxide. Since the waste heat has a high temperature it can also be used leading to a high overall efficiency. Material degradation and the cost of the components are the problems for the commercialisation of MCFC. Although there are companies around the world starting to commercialise MCFC some further cost reduction is needed before MCFC can be fully introduced at the market. In this work, alternative materials for three different components of MCFC have been investigated. The alternative materials should have a lower cost compared to the state-of-the-art materials but also meet the life-time goal of MCFC, which is around 5 years. The nickel dissolution of the cathode is a problem and a cathode with lower solubility is needed. The dissolution of nickel for three alternative cathode materials was investigated, where one of the materials had a lower solubility than the state-of-the-art nickel oxide. This material was also tested in a cell and the electrochemical performance was found to be comparable with nickel oxide and is an interesting candidate. An inexpensive anode current collector material is also desired. For the anode current collector, the contact resistance should be low and it should have good corrosion properties. The two alternative materials tested had low contact resistance, but some chromium enrichment was seen at the grain boundaries. This can lead to a decreased mechanical stability of the material. In the wet-seal area, the stainless steel used as bipolar/separator plate should be coated. An alternative process to coat the stainless steel, that is less expensive, was evaluated. This process can be a suitable process, but today, when the coating process is done manually there seems to be a problem with the adherence. This work has been a part of the IRMATECH project, which was financed by the European Commission, where the partners have been universities, research institutes and companies around Europe. / QC 20101123

The present study attempts to find an alternate computational tool to model the complex physical interactions within the molten salt FLiNaK in a way that is both efficient and accurate. Additionally, this study seeks to describe the effects of several different types of impurities on the FLiNaK salt system. This study selects two different polarizable force fields, the AMOEBA polarizable approach and the polarizable ion model, to determine the density and the structure of the impure FLiNaK salt mixtures at typical operating temperatures in molten salt reactors (between 500-900 °C). This study conducts ab initio molecular dynamics (AIMD) simulations and classical molecular dynamics (CMD) for these salt mixtures to determine the correct parameter set for these two force fields. This study also uses an optimizer to minimize the difference between the forces calculated with AIMD and CMD simulation data. The AMOEBA polarizable approach is able to predict density for FLiNaK; however, it is unable to reliably predict other thermophysical properties due to the instability of its CMD simulations. The polarizable ion model is able to reliably determine density and salt structure for pure and impure FLiNaK mixtures. This model can be further used to determine other thermophysical properties. The polarizable ion model predicted densities for four impure salt mixtures: FLiNaK-MoF3, FLiNaK-UF3, FLiNaK-CsF, and FLiNaK-ZrF4. The predicted densities at 700 °C given in kg/m3 are 1929.94, 2454.15, 1650.67, and 1961.87, respectively with an error compared to the additive density model of -2.51%, -5.79%, -17.15%, and -1.67%, respectively. This study presents the radial distribution function and density correlation functions for each salt mixture. This study also presents a discussion of the shortcomings of the AMOEBA polarizable approach, as well as further work that may be done with these tools.

Conducting research experiments on plutonium electrorefining is difficult due to the significant hazards and regulations associated with nuclear materials. Finding a surrogate for plutonium electrorefining studies would enable more fundamental research to be conducted. Potential surrogates were identified by determining the physical properties required to conduct electrorefining using a molten metal and molten salt in CaCl2 at 1123 K. More potential surrogates were identified by changing the matrix salt to be a LiCl-KCl-CaCl2 eutectic salt with electrorefining conducted at 673-773 K. Ce-CeCl3, In-InCl3, Zn-ZnCl2, Sn-SnCl2, and Bi-BiCl¬3 were investigated as potential plutonium electrorefining surrogates. Ce electrorefining in molten CaCl2 resulted in a difficult to separate colloid mixture of Ce, Ca and Cl. Electrorefining rates for In were too slow due to InCl3 volatilizing out of the molten salt. Zn was successfully electrorefined, but the metal obtained did not coalesce into one piece. Sn and Bi were successfully electrorefined and coalesced into solid product rings with high yields and coulombic efficiencies. While a surrogate could not be identified using the same conditions as plutonium electrorefining, two possible surrogates, Sn-SnCl2 and Bi-BiCl3,¬ were found that could imitate the physical configuration (i.e., molten salt on top of molten metal) of plutonium electrorefining at a reduced temperature using a eutectic LiCl-KCl-CaCl2 salt in place of CaCl2. Using this surrogate enables fundamental studies of aspects of plutonium electrorefining. One aspect of plutonium electrorefining research is to improve its efficiency and yield. Plutonium electrorefining is a time-intensive process which generates radioactive waste. Improvements in efficiency and yield can reduce process time and waste. One possible way of improving the efficiency of plutonium electrorefining is to study the impact of using an AC superimposed DC waveform. Four AC superimposed DC and two DC electrorefining runs were performed using bismuth as a plutonium surrogate. All six runs showed a high level of yield and coulombic efficiency. All six cathode rings were confirmed to be high-purity bismuth using scanning electron microscopy with energy dispersive x-ray analysis (SEM-EDS). While the results were inconclusive about the ability of AC superimposed DC waveforms to increase the efficiency of bismuth electrorefining, applying an AC superimposed DC waveform did not appear to decrease the efficiency or yield of the process. The change in waveform also did not result in impurities being present in the product cathode ring. Bismuth, in addition to being identified as a viable plutonium surrogate, has been investigated as a potential liquid electrode for molten salt electrorefining. Because of this, its electrochemical properties are of interest. However, bismuth's electrochemical behavior has received scant attention in eutectic LiCl-KCl melts and no studies were found in the ternary LiCl-KCl-CaCl2 melts. LiCl-KCl-CaCl2 melts offer some advantages over eutectic LiCl-KCl, such as lower melting point and higher oxide solubility. Cyclic voltammetry, square wave voltammetry, chronoamperometry, chronopotentiometry and open-circuit chronopotentiometry were used to measure electrochemical parameters, such as diffusivity and standard redox potential of bismuth electrodeposition in LiCl-KCl and LiCl-KCl-CaCl2 eutectics.

Molten salts are high-temperature heat transfer fluids intended for cooling and/or storage purposes in a variety of energy applications. The current work seeks to ultimately study the thermophysical properties of fluoride and chloride salts, which are commonly considered for use in advanced nuclear reactors. Thermophysical properties like thermal conductivity are fundamental to ensuring safe, efficient, and competitive designs for advanced commercial nuclear reactors. Measurement challenges with liquid salts such as electrical conduction, corrosion, convection, and thermal radiation have hindered traditional approaches in their attempts to accurately quantify these properties at high temperatures. Here, a needle probe is developed, which modifies principles from existing instrumental techniques in order to experimentally measure the thermal conductivity of molten salts with reduced error. An analytical heat transfer model is developed to characterize 1D radial heat flow in a multilayered cylindrical system. This includes a thin layer of salt located between the needle probe and a crucible to limit natural convection. After being validated with finite-element methods, the needle probe is used to measure the thermal conductivity of several reference liquids, whose thermophysical properties are well-established at low temperatures. These seven samples are water, sodium nitrate (molten salt), potassium nitrate (molten salt), toluene, ethanol, propylene glycol, and galinstan. The needle probe was able to accurately measure thermal conductivity between 0.40-0.66W/mK for these samples with 3.5-10% uncertainty. Three eutectic halide molten salts (presented by molar composition) were selected for high-temperature testing. These include the ternary fluorides LiF(46.5%)-NaF(11.5%)-KF(42%) and NaF(34.5%)-KF(59%)-MgF2(6.5%), as well as the binary chloride NaCl(58.2%)-KCl(41.8%). Because testing temperatures range between 500-750C, the governing model is adapted to account for radiative heat transfer through the salt sample in parallel with conductive heat transfer. Improvements to the experimental apparatus are also made. For all three salts, the needle probe accurately measured thermal conductivity between 0.490-0.849W/mK with total uncertainty generally being less than 20%. A linear fit to the data demonstrates a clear negative relationship between thermal conductivity and an increase in temperature, which agrees with theoretical and computational predictions. These results indicate that the needle probe successfully handles the assortment of measurement challenges associated with high-temperature molten salts and provides reliable data to create correlations for thermophysical property databases.

This work 1) draws insights on molten salt structure and properties directly from ab initio molecular dynamics (AIMD) simulations, 2) demonstrates the advantageous symbiosis of computational and experimental collaborations on molten salt research, and 3) simultaneously generates ab initio data sets for fitting an interatomic potential model for classical molecular dynamics (MD) simulations. This work discusses the motivations for AIMD simulations of molten salts, thermophysical properties and structural characteristics of interest, advanced methodologies for AIMD simulations, and several completed AIMD studies on molten salts. Of import are the methodological contributions of this work to AIMD simulations, primarily the radical increase in generalized gradient planewave energy cutoff used to more accurately model the electron distribution across a highly-polarizable molten salt. Cutoffs of up to 2500 Rydbergs are used in this work, but 2000 Rydbergs is found to be sufficient for most AIMD NpT modelling of molten fluorides. The equilibrium liquid density of eutectic FLiNaK as a function of temperature is found to agree with the experimental density reported by Chrenkova et al. to within 0.2%, and the equilibrium liquid density of eutectic FMgNaK is found to agree with experimental measurements reported herein to within 4%. Self-diffusion coefficients in FMgNaK are also considered, with applicability to other halide salts. Molybdenum, Cesium, iodide, nickel, hydrogen, oxide, and uranium complexation are examined. It is found that solvation strength can be qualitatively determine via AIMD simulations, and that poorly solvated solutes will minimize the surface area of interaction with the salt solution. Cesium in particular is shown to be volatile or retainable in FLiBe at 500, 650, and 800 ËšC based on complexation and validated experimentally. It is shown that the chemical potential of an anion varies between melts as influenced by the different cations present in each melt. Hence, attempts to use a common electrochemical reference reaction for different salt mixtures are at best an approximation.

This thesis investigates the possibility of using magnetic flow meters to measure the flowrate of molten salts in Seaborg Technologies Compact Molten Salt Reactor (CMSR).There is a need to accurately measure the flow rate in salt circulation systems to ensureproper operation of the entire facility. The requirements and criteria for the operationof a magnetic flow meter are studied, from which a model is constructed in COMSOLMultiphysics. The flow meter characteristics are analysed in COMSOL by performingsteady-state magnetohydrodynamic (MHD) simulations and by doing a sensitivity anal-ysis of the velocity field and the magnetic field strength. The induced electric potentialdifference in the flow meter when the reactor is at a maximum designed thermal power isin the range of 65 mV when using a normal inlet flow profile. The effect of the velocityfield is studied for two velocity profiles, and it indicates that the velocity profile alters theinduced potential difference even though the mass flowrate is the same. The magneticfield strength increases the electric potential difference when it is increasing, which isaccording to theory. The results indicate that magnetic flow meters are a viable optionfor Seaborg’s CMSR. However, further analysis is needed regarding the materials usedto ensure proper operation of the flow meter.

The ladle metallurgical furnace (LMF) is a very flexible and common unit operation found in most steelmaking melt shops, and enables the adjustment and fine-tuning of molten steel's composition and temperature prior to casting. Despite the importance of ladle metallurgy to the overall steel making process very little has been achieved in the way of advanced ladle control. Limited sensors are available to monitor heat progress during refining and current control methods involve manual procedures. This thesis represents part of an ongoing study on the modelling of a full-scale LMF in real-time with the forward goal of improved control and optimization. The first part of this thesis details a vision-based sensor for analyzing ladle eye dynamics online using a multivariate image analysis (MIA) technique based on principal component analysis (PCA). Predictive capabilities of the developed model are demonstrated using previously published cold model data over a wide range of operating variables. Further, preliminary work has confirmed the ability of the sensor for potential use in an industrial setting. The second part of this study concerns the development of metallurgical models for assessing the state of a ladle metallurgical furnace. Specifically, a multi-component kinetic model in combination with developed slag and steel thermodynamic solution models were used to quantitatively describe the kinetics of slag-metal reactions within 41 industrially sampled heats at ArcelorMittal Dofasco's LMF#2. Metal phase mass transfer coefficients for all elements in steel were assumed to follow the empirical relation derived from measured sulphur contents, while slag phase mass transfer coefficients were calculated by fitting the ratio of k^Mm/ k^MxOysl to the experimental results. On the basis of the fitted results, slag phase mass transfer coefficient correlations were evaluated using linear regression. Computed results from the model using these slag phase mass transfer coefficient correlations were found to be consistent with the experimental data. In regard to the developed thermodynamic solution models, original contributions to the modified interaction parameter formalism and cell model are presented. As process model predictions are invariably uncertain, the final part of this work involves the use of a stochastic model (extended Kalman filter) to account for process disturbances, model-mismatch and other sources of uncertainty that may result in significant error propagation causing poor process control and plant economics. Several case studies were performed to illustrate the effectiveness of the extended Kalman filter and its application to optimal sensor selection was introduced. / Thesis / Doctor of Philosophy (PhD)

This thesis documents research done for a transient hot wire system that will be used in future thermal conductivity measurements of molten salts. Research done with molten salts have been limited because of erroneous measurement capabilities, but the current research strives to introduce a new technique to accurately record thermal conductivity over a wide range of temperatures. This work follows up on past transient hot wire researchers whose designs and tests produced an instrument that can measure the thermal conductivity of molten metals up to 750 K. The transient hot wire (THW) technique has been selected to be used in molten salt to derive thermal conductivity values. While running a THW test in molten salts is outside the scope of this thesis, a modular system has been created for the use of running transient hot wire test that allows for a robust and repeatable testing. A PEGDA/galinstan sensor is used for the validation of the system. A robust GUI has been created to automate the experimental procedure in a glovebox environment. The inverse finite element method has been paired with a non linear fit script to optimize calculations and reduce run times. Test have been done to determine the thermal conductivity of PEGDA. The overall uncertainty of the thermal conductivity measured with the PEGDA sensor is estimated to be ±5% at a 95% confidence level. With a THW system implemented and validated a sensor has been designed to work in molten salts. A model has been created in two separate FEA programs to validate design changes and material properties. The sensor is made up of a chemical vapor deposition (CVD) diamond substrate and tungsten wires to overcome corrosion and heat challenges introduced when measuring molten salts. New manufacturing processes have been designed to allow the technique to use these materials in the THW sensor design. The selected material properties of the sensor and extensive finite element work have laid down the ground work for future experimentation and understanding of the thermal properties of molten salts. It is predicted that the CVD diamond (carbide) apparatus design will use the THW techniques to operate with an estimated accuracy of ±3% over a wide range of temperatures, from ambient up to 1200 K. Manufacturing of the diamond-tungsten sensor have proven the viability of depositing tungsten wire onto CVD diamond and growing a secondary layer of CVD diamond over the tungsten wire.

Over the past several years as interest in cleaner energy sources has grown nuclear power has come to the forefront. However, as interest in nuclear power grows so does the concern over the amount of high-level radioactive waste produced. Currently, the most popular way to deal with spent nuclear fuel is interim storage until a viable treatment option becomes available. Simply waiting for spent fuel to become safe to handle will take thousands of years and is not a reasonable long-term solution. We will soon run out of space in our spent fuel pools and while more dry storage space can be found it is not an ideal solution. One answer to this problem is the reprocessing of spent nuclear fuel. This could be done with either the plutonium uranium reduction extraction (PUREX) method or the pyroprocessing method. Since PUREX does not have the same level of built-in proliferation resistance as pyroprocessing, pyroprocessing is starting to be seen as a good alternative method. Pyroprocessing would take the spent nuclear fuel from a light water reactor and make it into a metal-based fuel that could be used in certain advanced reactors. Molten salt reactors are of particular interest when it comes to reprocessing spent nuclear fuel because of their unique property of using a liquid fuel. Molten salt reactors and spent fuel reprocessors could be directly connected which would save both time and money as little storage and transportation would need to be considered. Regardless of how and where the used nuclear fuel is being recycled it is important to be able to keep track of the major actinides and fission products in the fuel as it moves through the process. Electrochemical concentration measurements are straightforward and well understood in static cases when there is only a single element to consider. When additional elements are added, or the system is flowing rather than static, things get slightly more complicated but are still decently well understood. However, in the case of spent fuel reprocessing the system is both be flowing and contains much more than a single element. This case is not well understood and is what this study attempts to understand. Two different rotating electrodes were designed to simulate flowing conditions in an electrochemical cell. The first was a tungsten rotating disk electrode (RDE) and the second was a graphite RDE. We were not able to fully insulate the tungsten RDE and were therefore unable to achieve reliable results. Because of this the tungsten design was put aside in favor of the graphite design, which did prove to be sufficiently insulated. The graphite RDE was tested in two different salt systems: LiCl-KCl-NiCl2-CrCl2 and LiCl-KCl-EuCl3-SmCl3. In the nickel-chromium system the graphite RDE produced the expected results. The calculated nickel concentration was found to be within 10% of the measured concentration. Calculations of the chromium concentration, however, were not possible due to the deposition of nickel on the graphite surface, which increased the surface area of the working electrode. When the graphite RDE was tested in the second system it was first tested in the ternary salt LiCl-KCl-EuCl3 and was able to produce decent results. The concentration of europium calculated from the scan was within 10% of the measured value. When the RDE was tested in the LiCl-KCl-EuCl3-SmCl3 salt the results did not come out as expected. Several rather noisy CV curves were obtained and no alterations to the cell seemed to affect them. At this point it was determined that the reason for the confused scans was a connection problem that could not be remedied within the time frame of this study. While this study does not accomplish the task it set out to do, it is a good step in the direction toward understanding flowing systems containing more than a single element of interest and has successfully designed a reliable graphite RDE. / Master of Science / As interest in nuclear power continues to grow, so does the concern over the amount of high-level nuclear waste produced. More nuclear power means more nuclear reactors and thus more spent nuclear fuel to be dealt with. Currently most used nuclear fuel ends up in interim storage facilities where it is meant to wait until it is safe to handle, which could take several thousand years, or until a reliable disposal method is determined. On this path the amount of spent fuel that requires storage will quickly overrun the amount of storage space safely available. One way to reduce the amount of nuclear waste is to reprocess it to be used as fuel for different types of reactors. The pyroprocessing method takes the spent nuclear fuel from a typical light water reactor and recycles it into fuel that can be used in certain types of advanced reactors, such as molten salt reactors (MSR) and sodium-cooled fast reactors (SFR). The reprocessing system works to separate the usable actinide elements, such as uranium and plutonium, from any fission products or other contaminants. During these processes it is important to be able to keep track of the concentrations of each of these different elements to ensure proper separation. This study examines the use of two rotating disk electrode (RDE) designs that are meant to simulate the flowing conditions found in many reprocessing systems. These RDEs were to be used to measure the concentrations of different elements in molten salt systems. The first design, a tungsten RDE, could not be properly insulated and thus was unable to produce reliable results when tested in the electrochemical cell. The second design was a graphite RDE. This design did prove to be properly insulated and was able to produce good results when tested in the cell. The graphite RDE was tested in both LiCl-KCl-NiCl2-CrCl2 and LiCl-KCl-EuCl3-SmCl3. In the first system the concentration of nickel was correctly calculated using the data collected with the graphite RDE, while the chromium concentration could not be due to the nickel deposition on the graphite. In the second system, good results were obtained before the SmCl3 was added to the salt. At this point a connection error became apparent and reliable results were no longer possible. Further study is needed to understand the LiCl-KCl-EuCl3-SmCl3 system using the graphite RDE.

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