Nitride fuels have always been considered a good candidate for GENIV reactors, as well as space reactors, due to their high fissile density, highthermal conductivity and high melting point. In these concepts, not beingcompatible with water is not a significant problem. However, in recent years,nitride fuels started to raise an interest for application in thermal reactors,as accident tolerant or high performance fuels. However, oxide fuels havebenefited from decades of intensive research, and thousands of reactor-years.As such, a large effort has to be made on qualifying the fuel and developingtools to help assess their performances.In this thesis, the modeling side of this task is chosen. The effort istwo-fold: determining fundamental properties using atomistic models andputting together all the properties to predict the performances under irradi-ation using a fuel performance code. The first part is done combining manyframeworks. The density functional theory is the basis to compute the elec-tronic structure of the materials, to which a Hubbard correction is added tohandle the strong correlation effects. Negative side effects of the Hubbardcorrection are tackled using the so-called occupation matrix control method.This combined framework is first tested, and then used to find electronic andmechanic properties of the bulk material as well as the thermomechanicalbehavior of foreign atoms. Then, another method, the self-consistent meanfield (SCMF) one, is used to reach the dynamics properties of these foreignatoms. In the SCMF theory, the data that were obtained performing the abinitio simulations are treated to provide diffusion and kinetic flux couplingproperties.In the second step of the work, the fuel performance code TRANSURA-NUS is used to model complete fuel pins. An athermal fission gas releasemodel based on the open porosity is developed and tested on oxide fuels.A model for nitride fuels is introduced, and some correlations are bench-marked. Major issues remaining are pointed out and recommendations asto how to solve them are made. / <p>QC 20170227</p>

Investigation of nitride fuels and their properties has, for decades, been propelled on the basis of their desirable high metal densities and high thermal conductivities, both of which oer intrinsic advantages to performance, economy, and safety in fast and light water reactor systems. In this time several key obstacles have been identied as impeding the implementation of these fuels for commercial applications; namely chemical interactions with air and steam, the noted diculty in sintering of the material, and the high costs associated with the enrichment of 15N. The combination of these limitations, historically, led to the well founded conclusion that the most appropriate use of nitride fuels was in the fast reactor fuel cycle, where the cost burdens associated with them is substantially less. Indeed, it is within this context that the vast majority of work on nitrides has been and continues to be done. Nevertheless, following the 2011 Fukushima-Daiichi nuclear accident, a concerted governmental-industrial eort was embarked upon to explore the alternatives of so-called \accident tolerant" and \high performance" fuels. These fuels would, at the same time, improve the response of the fuel-clad system to severe accidents and improve the economy of operation for light water reactor systems. Among the various candidates proposed are uranium nitride, uranium silicide, and a third \uranium nitride-silicide" composite featuring a mixture of the former. In this thesis a method has been established for the synthesis, fabrication, and characterization of high purity uranium nitride, and uranium nitride-silicide composites, prepared by the spark plasma sintering (SPS) technique. A specic result has been to isolate the impact of the processing parameters on the microstructure of representative fuel pellets, essentially permitting any conceivable microstructure of interest to be fabricated. This has enabled the development of a highly reproducible technique for the production of pellets with microstructures tailored towards any desired porosity between 88-99.9%TD, any grain size between 6-24 μm, and, in the case of  the uranium nitride-silicide composite, a silicide-coated UN matrix. This has permitted the evaluation of these microstructural characteristics on the performance of these materials, specically with respect to their role as accident tolerant fuels. This has generated results which have tightly coupled nitride performance with pellet microstructure, with important implications for the use of nitrides in water-cooled reactors. / Under artionden har forskning om nitridbranseln och dess egenskaper bedrivits pa grundval av nitridbransletsatravarda egenskaper avseende dess hoga metall tathet och hog varmeledningsformaga. Dessa egenskaper besitter vasentliga fordelar avseende prestanda, ekonomi och sakerhet for metallkylda som lattvatten reaktorer. Genom forskning har aven centrala begr ansningar identierats for implementering av nitridbranslen for kommersiellt bruk. Begransningar avser den kemiska interaktionen med luft och vattenanga, en uppmarksammad svarighet att sintring av materialet samt hoga kostnader forknippade med den nodvandiga anrikningen av 15-N. Kombinationen av dessa begransningar resulterade, tidigare, i en valgrundad slutsats att nitridbranslet mest andamalsenliga anvandningsomrade var i karnbranslecykeln for snabba reaktorer. Detta da kostnaderna forenade med implementeringen av branslet ar avsevart lagre. Inom detta sammanhang har majoriteten av forskning avseende nitrider bedrivits och fortskrider an idag. Dock, efter karnkraftsolyckan i Fukushima-Daiichi 2011, inleddes en samlad industriell och statlig anstrangning for att undersoka alternativ till sa kallade \olyckstoleranta" och \hogpresterande" branslen. Dessa branslen skulle samtidigt forbattra reaktionstiden for bransleinkapsling systemet mot allvarliga olyckor samt forbattra driftsekonomin av lattvattenreaktorer. Foreslagna kandidater ar urannitrid, uransilicid och en tredje \uran nitrid-silicid", komposit bestaende av en blandning av de foregaende. Genom denna avhandling har en metod faststallts for syntes, tillverkning och karaktarisering av uran nitrid av hog renhet samt uran nitrid-silicid kompositer, forberedda med tekniken SPS (Spark Plasma Sintering). Ett specikt resultat har varit att isolera eekten av processparametrar pa mikrostrukturen pa representativa branslekutsar. Detta mojliggor, i princip, framstallningen av alla tankbara mikrostrukturer utav intresse for tillverkning. Vidare har detta mojliggjort utvecklingen av en hogeligen reproducerbar  teknik for framstallningen av branslekutsar med mikrostrukturer skraddarsydda for onskad porositet mellan 88 och 99.9 % TD, och kornstorlek mellan 6 och 24 μm. Dartill har en metod for att belagga en matris av uran nitrid-silicid framarbetats. Detta har mojliggjort utvarderingen av dessa mikrostrukturella parametrars paverkan pa materialens prestanda, sarskilt avseende dess roll som olyckstoleranta branslen. Detta har genererat resultat som ar tatt sammanlankat nitridbranslets prestanda till kutsens mikrostruktur, med viktiga konsekvenser for den potentiella anvandningen av nitrider i lattvatten reaktorer. / <p>QC 20170210</p>

Thermal conductivity is a crucial parameter for nuclear fuel, as it sets an upper limit on reactor operating temperature to have safety margins. Uranium mononitride (UN) is a prospective fuel for fast reactors, for which limited experimental studies have been conducted, compared to the currently dominating light-water reactor fuel, uranium dioxide. The aim of this thesis is to determine the thermal conductivity in UN and to determine its porosity dependence. This was done by manufacturing dense and porous high-purity samples of UN and examining them with laser flash analysis, which with data on specific heat and thermal expansion gives the thermal conductivity. To analyse the result, a theoretical study of the phenomenology of thermal conductivity as well as a review and comparison with previous investigations were carried out. The porosity range was 0.1–31% of theoretical density. Thermal diffusivity data from laser flash analysis, thermal expansion data and specific heat data was collected for 25–1400 C. The laser flash data had high discrepancy at higher temperatures due to thermal instability in the device and deviations due to graphite deposition on the samples, but the low temperature data should be reliable. As the specific heat data was also of poor quality, literature data was used instead. As for the thermal diffusivity data, the calculated thermal conductivity for lower temperatures are more accurate. A modified version of the porosity model by Ondracek and Schulz was used to analyse the porosity dependence of the thermal conductivity, taking into account the different impacts of open and closed porosity. / Värmeledningsförmåga är en avgörande egenskap för kärnbränslen, eftersom det begränsar den maximala drifttemperaturen i reaktorn för att ha säkerhetsmarginaler. Uranmononitrid (UN) är ett framtida bränsle för snabba reaktorer. Jämfört med det dominerande bränslet i lättvattenreaktorer, urandioxid, har endast begränsade experimentella studier gjorts av UN. Målet med detta arbete är att bestämma värmeledningsförmågan i UN och bestämma dess porositetsberoende. Detta gjordes genom att tillverka kompakta och porösa prover av UN och undersöka dem med laserblixtmetoden, vilket tillsammans med värmekapacitet och värmeutvidgning ger värmeledningsförmågan. För att analysera resultatet gjordes en teoretisk studie av värmeledning såväl som en genomgång av och jämförelse med tidigare undersökningar. Provernas porositet sträckte sig från 0.1% till 31% av teoretisk densitet. Värmediffusivitetsdata från laserblixtmetoden, värmeutvidgningsdata och värmekapacitetsdata samlades in för 25–1400 C. Värdena från laserblixtmätningen hade hög diskrepans vid höga temperaturer p.g.a. termisk instabilitet i anordningen och avvikelser p.g.a. grafitavlagring på proverna, men data för låga temperaturer borde vara tillförlitliga. Eftersom resultaten från värmekapacitetsmätningen var av dålig kvalité, användes litteraturdata istället. Som en konsekvens av bristerna i mätningen av värmediffusivitet är presenterade data för värmeledningsförmåga mest exakta för låga temperaturer. En modifierad version av Ondracek-Schulz porositetsmodell användes för att analysera värmeledningsförmågans porositetsberoende genom att ta hänsyn till olika inverkan av öppen och sluten porositet.

<p>QC 20150603</p>

The effect of proton (H+) irradiation on uranium mononitride (UN) and UN compositefuel with 10 at.% ZrN (UN10at%ZrN) was examined. Protons of 2 MeV with fluences of1E17, 1E18, 1E19 and 1E20 ions/cm2 were accelerated towards the fabricated samples in orderto investigate the evolution of the micro-structure. Stopping and Range of Ions in Matter(SRIM) calculations were performed to determine the displacements per atom associatedwith the depth of the highest damage, for each fluence.X-Ray diffraction (XRD) was used in both samples to identify the chemical composition ofeach pellet, which revealed the low presence of oxygen. Based on scanning electron microscopy(SEM), deterioration of the samples surface was observed, as the proton fluence increased.The applied stress due to the irradiation, led to the cracking of the pellets at the highestfluences. Blisters and craters appear to surround the cracked region, which might originatefrom the significant levels of hydrogen implantation within the samples.From Electron backscatter diffraction (EBSD) analysis, the grain size of the UN10at%ZrNcomposite was found to be smaller than in UN, due to the nano-particle nature of the ZrNpowder. The latter technique was also used to observe the elevated irradiated regions, whichwere further investigated by atomic force microscopy (AFM). Nano-indentation detectedirradiation hardening for both samples in the irradiated regions. Focused ion beam (FIB)milling was applied to remove lamellas from the cracked regions in both UN and compositesamples in order to be analyzed by transmission electron microscopy (TEM). The latter mightreveals the formation of dislocation loops in the irradiated areas. / Effekten av protonbestrålning på urannitrid (UN) och UN-kompositbränsle med 10 at.% ZrN (UN10at%ZrN) undersöktes. Protoner på 2 MeV med total dos på 1E17, 1E18, 1E19 och 1E20 joner/cm2 accelererades mot de tillverkade proverna för att undersöka utvecklingen av mikrostrukturen under bestrålning. SRIM-beräkningar (Stopping and Range of Ions in Matter) utfördes för att bestämma profilen på skadan och jonimplanteringen i förhållande till djupet, för varje dosnivå.  Röntgendiffraktion (XRD) användes på båda proverna för att identifiera den kemiska sammansättningen av varje kuts, vilket visade att syrehalten var låg. Med hjälp av svepelektronmikroskopi (SEM) observerades en försämring av provernas yta när protonflödet ökade. Den resulterande mekaniska spänningen överskred provets brottstyrka på djupet, eftersom nitriderna inte är så duktila, vilket ledde till sprickbildning i proverna som utsattes för de högsta doserna. Blåsor och kratrar omger det spruckna området, vilket beror på betydande väteimplantering i provet.  Genom electron backscatter diffraction analys (EBSD) konstaterades att kornstorleken hos UN10at%ZrN-kompositen var mindre än hos UN, på grund av ZrN-pulvrets nanopartikelnatur. Den sistnämnda tekniken användes för att observera de högt bestrålade områdena, som undersöktes ytterligare med Atomic force microscopy (AFM). Genom nano-indientation upptäcktes bestrålningshärdning för båda proverna i de bestrålade områdena. Fräsning med en fokuserad jonstråle (FIB) användes för att avlägsna lameller från de spruckna områdena i både UN- och kompositprovet för att kunna analyseras med transmission electron microscopy (TEM). Det senare visade att det bildades dislokationer i de bestrålade områdena.

This thesis project aims to develop an innovative technique for the production of high-purity uranium nitride (UN) through the ammonolysis of fluorides. The desired objective is to perform a controlled gas/gas reaction between uranium hexafluoride (UF6) and ammonia (NH3) at 800°C. The intermediate product thereby obtained (uranium dinitride, UN2) is subjected to further heating up to 1100°C under argon atmosphere, to ultimately produce UN. An inherent challenge faced in previous experiments was related to the dissociation of ammonia, which is alimiting factor for upscaling. Therefore, in this project a new setup is invented to address this challenge and it is proved experimentally: the idea is to achieve a coaxial laminar flow of UF6 and a carrier gas, where a central stream of the former is shielded by the latter so that the tworeacting gasses mix only in the hot point of the furnace, where the desired reaction can happen. To implement this approach, the ammonia dissociation has been studied, an apparatus for the controlled evaporation of UF6 has been designed and built, and two different injection nozzleshave been tested in different setup configurations. Eventually, the complete prototype has been tested altogether in a synthesis experiment at 800°C, and the products thus obtained have been converted into UN at 1100°C. Numerous auxiliary experiments have been performed using UF4as a reactant, as it is easier to handle and the results thus obtained can be largely extended to UF6. Lastly, a UF4 synthesis experiment has been performed, as educationally helpful to further dig into some chemistry features of this material, and a UN pellet has been sintered with Spark Plasma Sintering (SPS). / Detta examensarbete syftar till att utveckla en innovativ teknik för framställning av urannitrid (UN) med hög renhet genom ammonolys av fluorider. Målsättningen med arbetet är att utföra en kontrollerad gas/gasreaktion mellan uranhexafluorid (UF6) och ammoniak (NH3) vid 800°C. Den därigenom erhållna mellanprodukten (urandinitrid, UN2) värms därefter upp till 1100°C i en argonatmosfär, för att slutligen producera UN. En utmaning i tidigare experiment var relaterat till dissociationen av ammoniak, vilket är en begränsande faktor för uppskalning av processen. För att möta denna utmaning utvecklas därför en ny process i detta projekt och den bevisas experimentellt. Tanken är att skapa ett koaxiellt laminärt flöde bestående av UF6 och en bärgas, där en central ström av den första är avskärmad av det senare så att de två reagerande gaserna enbart blandas i ugnens heta zon, där den önskade reaktionen sker. För att implementera denna metod så har ammoniakdissociationen studerats, en apparat för kontrollerad avdunstning av UF6 har designats och byggts, och två olika insprutningsmunstycken har testats i olika konfigurationer. Den kompletta prototypen har testats i sin helhet med ett syntesexperiment vid 800°C, och produkterna som erhållits har konverterats till UN vid 1100°C. Ett flertal hjälpexperiment har utförts med UF4 som reaktant, eftersom den är enklare att hantera, och de erhållna resultaten kan till stor del utvidgas till UF6. Slutligen har ett UF4-syntesexperiment genomförts för att som ett pedagogiskt hjälpmedel ytterligare studera vissa kemiska egenskaper hos detta material. En UN-pellet har sintrats med starkströmsassisterad varmpressning (eng. Spark Plasma Sintering, SPS).

In this work a manufacturing method for UN, ZrN and (U,Zr)N pellets was established at the nuclear fuel laboratory at KTH Stockholm/Sweden, which consists of the production of nitride powders and their sintering into pellets by spark plasma sintering. The nitride powders were produced by the hydriding-nitriding route using pure metal as starting material. This synthesis was performed in a stream of the particular reaction gas. A synthesis control and monitoring system was developed, which can follow the reactions in real time by measuring the gas flow difference before and after the reaction chamber. With the help of this system the hydriding and nitriding reactions of uranium and zirconium were studied in detail. Fine nitride powders were obtained; however, the production of zirconium nitride involved one milling step of the brittle zirconium hydride. Additionally uranium and zirconium alloys with different zirconium contents were produced and synthesized to nitride powders. It was found that also the alloys could be reduced to fine powder, but only by cyclic hydriding-dehydriding. Pellets were sintered out of uranium nitrides, zirconium nitrides, mixed nitrides and alloy nitrides. These experiments showed that relative densities of more than 90% can easily be achieved for all those powders. Pellets sintered from mechanically mixed nitride powders were found to still consist of two separate nitride phases, while nitride produced from alloy was demonstrated to be a monophasic solid solution both as powder and as sintered pellets.

Metallic fuels were produced through arc-melting. As-cast phases, microstructuresand selected mechanical properties were investigated for UZr,U-Th, and U-Th-Zr systems. For each system, two compositions wereinvestigated, with approximately 5 at. % and 20 at. % solute material, for atotal of six alloys. As-cast alloy microstructures were assessed in the contextof their equilibrium systems and compared to relevant published works whereapplicable. Mechanical testing revealed increased hardness with increasingsolute concentration, compared to the reference materials. The results supportthe conclusion that solid solution strengthening is the primary mechanismenabling this change in each binary system.Additionally, (U,Zr)N fuel was synthesized. This work exemplified aprocess to produce fuel with a homogeneous distribution of zirconium in thefuel matrix, thus representing a simulated burn-up distribution of zirconium.Refinements can be made to further improve this process in future work. Thesefindings will support a broader separate effects testing campaign underway bythe SUNRISE centre / Metalliska bränslen framställdes genom bågsmältning. Som gjutna faser,mikrostrukturer och utvalda mekaniska egenskaper undersöktes för U-Zr-, UTh-och U-Th-Zr-system. För varje system undersöktes två sammansättningar,med cirka 5 at. % och 20 at. % löst material, för totalt sex legeringar.Mikrostrukturer av gjutna legeringar diskuterades i samband med derasjämviktssystem och jämfördes med literattur. Mekanisk testning visadeökad hårdhet med ökad halt lösta atomer, jämfört med råvarorna. Denprimära mekanismen som möjliggör denna förändring föreslogs vara solidlösningsförstärkning.Vidare syntetiserades (U,Zr)N-bränsle. Detta arbete exemplifierade enprocess för att producera bränsle med en homogen fördelning av zirkoniumi bränslematrisen, vilket representerar en simulerad utbränningsfördelning avzirkonium. Denna process kan förbättras. Resultaten stödjer en bredare separateffekttestningskampanj som SUNRISE-centret arbetar med.