UN microspheres embedded in UO2 matrix: an innovative accident tolerant fuel

Uranium nitride (UN)-uranium dioxide (UO2) composite fuels are being considered as an accident tolerant fuel (ATF) option for light water reactors. However, the complexity related to the chemical interactions between UN and UO(2 )during sintering is still an open problem. Moreover, there is a lack of knowledge regarding the influence of the sintering parameters on the amount and morphology of the alpha-U2N3 phase formed. In this study, a detailed investigation of the interaction between UN and UO2 is provided and a formation mechanism for the resulting alpha-U2N3 phase is proposed. Coupled with these analyses, an innovative ATF concept was investigated: UN microspheres and UO2,13 powder were mixed and subsequently sintered by spark plasma sintering. Different temperatures, pressures, times and cooling rates were evaluated. The pellets were characterised by complementary techniques, including XRD, DSC, and SEM-EDS/WDS/EBSD. The UN and UO2 interaction is driven by O diffusion into the UN phase and N diffusion in the opposite direction, forming a long-range solid solution in the UO2 matrix, that can be described as UO2-xNx. The cooling process decreases the N solubility in UO2-xNx, causing then N redistribution and precipitation as alpha-U2N3 phase along and inside the UO2 grains. This precipitation mechanism occurs at temperatures between 1273 K and 973 K on cooling, following specific crystallographic grain orientation patterns. (C) 2020 The Authors. Published by Elsevier B.V

Oxidation of UN-U2N3/UO2 composites: an evaluation of UO2 as an oxidation barrier for the nitride phases

Composite fuels such as UN-UO2 are being considered to address the lower oxidation resistance of the UN fuel from a safety perspective for use in light water reactors, whilst improving the in-reactor behaviour of the more ubiquitous UO2 fuel. An innovative UN-UO2 accident tolerant fuel has recently been fabricated and studied: UN microspheres embedded in UO2 matrix. In the present study, detailed oxidative thermogravimetric investigations (TGA/DSC) of high-density UN/U2N3-UO2 composite fuels (91-97 %TD), as well as post oxidised microstructures obtained by SEM, are reported and analysed. Triplicate TGA measurements of each specimen were carried out at 5 K/min up to 973 K in a synthetic air atmosphere to assess their oxidation kinetics. The mass variation due to the oxidation reactions (%), the oxidation onset temperatures (OOTs), and the maximum reaction temperatures (MRTs) are also presented and discussed. The results show that all composites have similar post oxidised microstructures with mostly intergranular cracking and spalling. The oxidation resistance of the pellet with initially 10 wt% of UN microspheres is surprisingly better than the UO2 reference. Moreover, there is no significant difference in the OOT (~557 K) and MRT (~615 K) when 30 wt% or 50 wt% of embedded UN microspheres are used. Therefore, the findings in this article demonstrate that the UO2 matrix acts as a barrier to improve the oxidation resistance of the nitride phases at the beginning of life conditions

Comparing CrN and TiN Coatings for Accident-Tolerant Fuels in PWR and BWR Autoclaves

The development of coatings for accident-tolerant fuels (ATFs) for light water reactor (LWR) applications promises improved corrosion resistance under accident conditions and better performances during operation. CrN and TiN coatings are characterized by high wear resistance coupled with good corrosion resistance properties. They are generally used to protect materials in applications where extreme conditions are involved and represent promising candidates for ATF. Zr cladding tubes coated with 5 \ub5m-thick CrN or TiN, exposed in an autoclave to simulated PWR chemistry and BWR chemistry, were characterized with SEM, EDS, and STEM. The investigation focused on the performance and oxidation mechanisms of the coated claddings under simulated reactor chemistry. Both coatings provided improved oxidation resistance in a simulated PWR environment, where passivating films of Cr2O3\ua0and TiO2, less than 1 \ub5m-thick, formed on the CrN and TiN outer surfaces, respectively. Under the more challenging BWR conditions, any formed Cr2O3\ua0dissolved into the oxidizing water, resulting in the complete dissolution of the CrN coating. For the TiN coating, the formation of a stable TiO2\ua0film was observed under BWR conditions, but the developed oxide film was unable to stop the flux of oxygen to the substrate, causing the oxidation of the substrate

Coated ZrN sphere-UO2 composites as surrogates for UN-UO2 accident tolerant fuels

Uranium nitride (UN) spheres embedded in uranium dioxide (UO2) matrix is considered an innovative accident tolerant fuel (ATF). However, the interaction between UN and UO2 restricts the applicability of such composite in light water reactors. A possibility to limit this interaction is to separate the two materials with a diffusion barrier that has a high melting point, high thermal conductivity, and reasonably low neutron cross-section. Recent density functional theory calculations and experimental results on interface interactions in UN-X-UO2 systems (X = V, Nb, Ta, Cr, Mo, W) concluded that Mo and W are promising coating candidates. In this work, we develop and study different methods of coating ZrN spheres, used as a surrogate material for UN spheres: first, using Mo or W nanopowders (wet and binder); and second, using chemical vapour deposition (CVD) of W. ZrN-UO2 composites containing 15 wt% of coated ZrN spheres were consolidated by spark plasma sintering (1773 K, 80 MPa) and characterised by SEM/FIB-EDS and EBSD. The results show dense Mo and W layers without interaction with UO2. Wet and binder Mo methods provided coating layers of about 20 mu m and 65 mu m, respectively, while the binder and CVD of W methods layers of about 12 mu m and 3 mu m, respectively

CrN–NbN nanolayered coatings for enhanced accident tolerant fuels in BWR

The accident tolerant fuel (ATF) concept has emerged in the years after the 2011 Fukushima accident as part of a renewed effort in research for light water reactors. The primary focus is to further improve safety measures under and beyond design basis accident conditions, and to improve fuel cladding performance in normal operation. The application of a coating on zirconium claddings can achieve both these aims without extensive changes to the reactor design. Metallic chromium coatings have been profusely studied as solution for pressurized water reactors, but the search for an effective ATF coating able to withstand the environment inside boiling water reactors (BWRs) is still ongoing. In this work, two different versions of a novel nitride coating composition were studied. Zirconium claddings coated with 8 µm thick layers of superlattice CrN–NbN and a nanolayered CrN–NbN were tested in autoclave under BWR operating conditions for 60 days. Scanning electron microscopy, transmission electron microscopy, energy dispersive x-ray spectroscopy, electron back-scattered diffraction, x-ray diffraction, and atom probe tomography were employed to characterize as-deposited and autoclaved samples of these two materials. During exposure, both coating versions formed a stable, dense and passivating oxide scale (200–300 nm thick) on the surface, demonstrating improved oxidation protection under operating conditions. Some differences in the oxide growth mechanism were observed between the superlattice and the nanolayered CrN–NbN coatings, which allowed to glimpse at the effect of the layer thickness on the oxidation protection provided by these coatings. The nano-structured morphology of both coatings remained unaffected by the autoclave test, but a 35 nm thick Zr-Cr-N phase was found at the coating-substrate interface of the superlattice CrN–NbN coated cladding

CrN–NbN nanolayered coatings for enhanced accident tolerant fuels in BWR

The accident tolerant fuel (ATF) concept has emerged in the years after the 2011 Fukushima accident as part of a renewed effort in research for light water reactors. The primary focus is to further improve safety measures under and beyond design basis accident conditions, and to improve fuel cladding performance in normal operation. The application of a coating on zirconium claddings can achieve both these aims without extensive changes to the reactor design. Metallic chromium coatings have been profusely studied as solution for pressurized water reactors, but the search for an effective ATF coating able to withstand the environment inside boiling water reactors (BWRs) is still ongoing. In this work, two different versions of a novel nitride coating composition were studied. Zirconium claddings coated with 8 \ub5m thick layers of superlattice CrN–NbN and a nanolayered CrN–NbN were tested in autoclave under BWR operating conditions for 60 days. Scanning electron microscopy, transmission electron microscopy, energy dispersive x-ray spectroscopy, electron back-scattered diffraction, x-ray diffraction, and atom probe tomography were employed to characterize as-deposited and autoclaved samples of these two materials. During exposure, both coating versions formed a stable, dense and passivating oxide scale (200–300 nm thick) on the surface, demonstrating improved oxidation protection under operating conditions. Some differences in the oxide growth mechanism were observed between the superlattice and the nanolayered CrN–NbN coatings, which allowed to glimpse at the effect of the layer thickness on the oxidation protection provided by these coatings. The nano-structured morphology of both coatings remained unaffected by the autoclave test, but a 35 nm thick Zr-Cr-N phase was found at the coating-substrate interface of the superlattice CrN–NbN coated cladding

Microstructural characterization of uranium-rich alloys of the system U-Nb-Zr.

Foi efetuada a caracterização microestrutural de 10 ligas dos sistemas urânio-nióbio (U-10Nb; U-15Nb; U-20Nb), urânio-zircônio (U- 10Zr; U-15Zr, U-20Zr) e urânio-nióbio-zircônio (U-2,5Nb-2,5Zr; U-5Nb- 5Zr; U-7,5Nb-7,5Zr; U-10Nb-10Zr), no canto rico em urânio. As ligas estudadas são candidatas ao uso como elementos combustíveis tipo placa, utilizados tanto em reatores nucleares de pesquisa como em reatores nucleares de potência. As ligas foram preparadas por fusão a plasma em forno com eletrodo não consumível de tungstênio. Após várias fusões, as amostras sofreram tratamento térmico de homogeneização a 1000ºC por 96 horas, com resfriamento em água. Em seguida, as amostras homogeneizadas foram recozidas a 700 e a 500ºC, com resfriamento em água. No total, foram estudadas 40 amostras de 10 ligas diferentes em 4 condições diferentes: bruto de fundição, homogeneizadas a 1000ºC e envelhecidas a 700 e a 500ºC. Foram utilizadas várias técnicas complementares de caracterização microestrutural: microscopia óptica, microscopia eletrônica de varredura com auxilio de microanálise por dispersão de energia de raios X, difração de raios X com auxílio do método de análise de Rietveld, e medidas de microdureza Vickers. Os resultados mostraram que os elementos de liga Nb e Zr estabilizam a fase alotrópica &#947 do urânio e atrasam a transformação de γ para β. Neste aspecto, o Nb é mais eficaz que o Zr. Além disto, podem ocorrer durante o resfriamento transformações martensíticas γ→α\', β→α′ e possivelmente γ→γ°. A temperatura de início de transformação martensítica (Ms) formadora da fase diminui com a adição dos elementos de liga estudados. Ms intercepta a temperatura ambiente entre as composições U-5Nb-5Zr e U-7,5Nb-7,5Zr. Foi verificado também que a reação peritetóide α + γ2→ δ do sistema U-Zr possui uma cinética lenta e não pode ser detectada nos tempos e temperaturas estudados. Em algumas ligas foi possível reter na temperatura ambiente ligas com microestrutura martensítica dúcteis, que permitem a conformação mecânica a frio, o que é de significativo interesse tecnológico.The microstructures of 10 uranium-rich alloys of the uraniumniobium (U-10Nb; U-15Nb; U-20Nb), uranium-zirconium (U-10Zr; U- 15Zr;U-20Zr) and uranium-niobium-zirconium (U-2.5Nb-2.5Zr; U-5Nb-5Zr; U-7.5Nb-7.5Zr; U-10Nb-10Zr)systems have been characterized. The studied alloys are considered for plate-type nuclear fuels fabrication used both in nuclear research reactors and in nuclear power reactors. The alloys were melted by arc plasma methods employing nonconsumable tungsten cathode. After several fusions, samples were subjected to homogenizing heat treatment at 1000ºC for 96 hours and then quenched in water. Then the samples were annealed at 700 and 500ºC. The microstructural characterization encompassed 40 samples of 10 different alloys composition in four different conditions: as cast, homogenized at 1000°C and aged at 700 and 500ºC. Microstructural characterization was performed using several complementary techniques: optical microscopy; scanning electron microscopy with energy-dispersive X-ray analysis; X-ray diffraction with the aid of the Rietveld analysis method; and Vickers microhardness measurements. The results showed that the Nb and Zr additions have stabilized the uranium γ-phase and delayed the γ and β phase transformation. In this regard, Nb was more effective than Zr. However, during cooling martensitic transformations γ→α\', β→α\' and possibly γ→γ° may occur. The martensitic transformation start temperature (Ms), which produces the phase , decreased with Nb and Zr additions. Ms intersected room temperature between the compositions U-5Nb-5Zr e U- 7,5Nb-7,5Zr. It was found that the peritectoid reaction α + γ2 → δ of the U-Zr system showed a very slow kinetics and could not be detected in the range of the studied times and temperatures. An important result of the technological point of view is that in some alloys it was possible to retain at room temperature a ductile martensitic microstructure, allowing cold forming

Microstructural characterization of uranium-rich alloys of the system U-Nb-Zr.

Foi efetuada a caracterização microestrutural de 10 ligas dos sistemas urânio-nióbio (U-10Nb; U-15Nb; U-20Nb), urânio-zircônio (U- 10Zr; U-15Zr, U-20Zr) e urânio-nióbio-zircônio (U-2,5Nb-2,5Zr; U-5Nb- 5Zr; U-7,5Nb-7,5Zr; U-10Nb-10Zr), no canto rico em urânio. As ligas estudadas são candidatas ao uso como elementos combustíveis tipo placa, utilizados tanto em reatores nucleares de pesquisa como em reatores nucleares de potência. As ligas foram preparadas por fusão a plasma em forno com eletrodo não consumível de tungstênio. Após várias fusões, as amostras sofreram tratamento térmico de homogeneização a 1000ºC por 96 horas, com resfriamento em água. Em seguida, as amostras homogeneizadas foram recozidas a 700 e a 500ºC, com resfriamento em água. No total, foram estudadas 40 amostras de 10 ligas diferentes em 4 condições diferentes: bruto de fundição, homogeneizadas a 1000ºC e envelhecidas a 700 e a 500ºC. Foram utilizadas várias técnicas complementares de caracterização microestrutural: microscopia óptica, microscopia eletrônica de varredura com auxilio de microanálise por dispersão de energia de raios X, difração de raios X com auxílio do método de análise de Rietveld, e medidas de microdureza Vickers. Os resultados mostraram que os elementos de liga Nb e Zr estabilizam a fase alotrópica &#947 do urânio e atrasam a transformação de γ para β. Neste aspecto, o Nb é mais eficaz que o Zr. Além disto, podem ocorrer durante o resfriamento transformações martensíticas γ→α\', β→α′ e possivelmente γ→γ°. A temperatura de início de transformação martensítica (Ms) formadora da fase diminui com a adição dos elementos de liga estudados. Ms intercepta a temperatura ambiente entre as composições U-5Nb-5Zr e U-7,5Nb-7,5Zr. Foi verificado também que a reação peritetóide α + γ2→ δ do sistema U-Zr possui uma cinética lenta e não pode ser detectada nos tempos e temperaturas estudados. Em algumas ligas foi possível reter na temperatura ambiente ligas com microestrutura martensítica dúcteis, que permitem a conformação mecânica a frio, o que é de significativo interesse tecnológico.The microstructures of 10 uranium-rich alloys of the uraniumniobium (U-10Nb; U-15Nb; U-20Nb), uranium-zirconium (U-10Zr; U- 15Zr;U-20Zr) and uranium-niobium-zirconium (U-2.5Nb-2.5Zr; U-5Nb-5Zr; U-7.5Nb-7.5Zr; U-10Nb-10Zr)systems have been characterized. The studied alloys are considered for plate-type nuclear fuels fabrication used both in nuclear research reactors and in nuclear power reactors. The alloys were melted by arc plasma methods employing nonconsumable tungsten cathode. After several fusions, samples were subjected to homogenizing heat treatment at 1000ºC for 96 hours and then quenched in water. Then the samples were annealed at 700 and 500ºC. The microstructural characterization encompassed 40 samples of 10 different alloys composition in four different conditions: as cast, homogenized at 1000°C and aged at 700 and 500ºC. Microstructural characterization was performed using several complementary techniques: optical microscopy; scanning electron microscopy with energy-dispersive X-ray analysis; X-ray diffraction with the aid of the Rietveld analysis method; and Vickers microhardness measurements. The results showed that the Nb and Zr additions have stabilized the uranium γ-phase and delayed the γ and β phase transformation. In this regard, Nb was more effective than Zr. However, during cooling martensitic transformations γ→α\', β→α\' and possibly γ→γ° may occur. The martensitic transformation start temperature (Ms), which produces the phase , decreased with Nb and Zr additions. Ms intersected room temperature between the compositions U-5Nb-5Zr e U- 7,5Nb-7,5Zr. It was found that the peritectoid reaction α + γ2 → δ of the U-Zr system showed a very slow kinetics and could not be detected in the range of the studied times and temperatures. An important result of the technological point of view is that in some alloys it was possible to retain at room temperature a ductile martensitic microstructure, allowing cold forming

Interaction between precipitation and recrystallization in alloy uranium containing niobium and zirconium (Mulberry alloy).

No presente trabalho foram estudados os fenômenos de encruamento e, principalmente, transformação de fases, recuperação e recristalização, presentes na liga U-7,5Nb-2,5Zr (Mulberry alloy) e no urânio não ligado. Realizou-se a fusão da liga por dois métodos: plasma (menor massa) e indução (maior massa). A caracterização microestrutural das ligas resultantes nos estados bruto de fundição e homogeneizado (tratado termicamente na região da fase γ seguido de resfriamento rápido em água), assim como do urânio em seu estado inicial, foi realizada com auxílio de várias técnicas complementares de análise microestrutural. No estado gama estabilizado, a liga U-7,5Nb-2,5Zr foi deformada na temperatura ambiente por dois métodos: laminação a frio, dividida em vários estágios (20%, 50%, 60% e 80%), e limagem, sendo o pó resultante de alto grau de deformação. As amostras deformadas foram posteriormente recozidas em tratamentos isócronos (1 hora) e isotérmicos (200ºC, 450ºC e 700ºC). O urânio não ligado foi deformado em aproximadamente 60% e 80% de redução em espessura, e em seguida submetido a tratamentos isócronos (1 hora) e isotérmicos (400ºC e 650ºC). Os fenômenos de encruamento, recuperação, recristalização e transformação de fases foram estudados predominantemente por microscopia óptica, dureza e difração de raios X, com auxílio do método de Rietveld. Adicionalmente, técnicas de análise térmica (dilatometria e calorimetria diferencial) foram utilizadas para acompanhamento da cinética de transformação de fase e energia armazenada na deformação. Com relação à deformação, a liga U-7,5Nb-2,5Zr mostrou ser capaz de sofrer reduções da ordem de 70% na temperatura ambiente, sem necessidade de recozimentos intermediários e com um baixo grau de encruamento. Similarmente, o urânio não ligado mostrou ser capaz de sofrer graus de deformação mais altos na temperatura ambiente, entretanto, este material apresentou alto grau de encruamento e, mesmo após considerável grau de deformação, ainda apresentava muitas heterogeneidades de deformação, como bandas de deformação e maclas. Foi observado que a recristalização do urânio não ligado teve início a aproximadamente 454ºC. Para a liga no estado deformado e supersaturado, a precipitação de fases tende a ocorrer antes da recristalização. Assim, o comportamento desta liga sob aquecimento pós-deformação pode ser resumido da seguinte forma: ~200°C (Recuperação) ---> 300-575°C (Precipitação de fases) ---> 575°C (Recristalização). O rápido aquecimento para temperaturas acima de 650ºC, ou a manutenção desta temperatura por longos tempos, gera uma estrutura γ recristalizada com grãos equiaxiais. Uma estrutura de grãos finos (~8,3µm) foi obtida no recozimento a 700ºC/1h tanto para baixo como para alto grau de deformação. Uma taxa de aquecimento lenta, ou recozimento na faixa de 300-575ºC, gera precipitação da fase antes da recristalização. Consequentemente, a transformação eutetóide γ→α+γ₃ ocorre de modo a herdar a orientação do grão γ deformado, o que pode gerar uma textura de transformação. Na faixa de temperaturas de 575-650ºC ocorre a interação entre os fenômenos de precipitação de fase e recristalização. Em recozimentos a 200ºC foi possível observar a predominância da recuperação para graus de deformação intermediários (60%) e altos (80%), mas para grau de deformação baixo (20%) prevaleceu endurecimento por precipitação da fase α\'\'. Com auxílio da análise em um calorímetro diferencial (DSC) foi observado que a energia armazenada na deformação e liberada durante o processo de recristalização da liga U-7,5Nb-2,5Zr foi de 6,5J/g. Tal valor é relativamente alto se comparado aos metais comuns, o que leva à suposição de que uma linha de discordância no urânio representa uma maior energia. Este fato tem influência direta no processo recristalização. Este experimento demonstrou também que os fenômenos de precipitação de fase e recristalização interagem entre si, com relação à energia disponível para o processo. A textura da liga U-7,5Nb-2,5Zr foi estudada por difração de raios X (DRX) nas condições com fase γ estabilizada (obtida através de fusão, coquilhamento e homogeneização seguida de têmpera) e no estado deformado (laminado a temperatura ambiente). A liga na condição com γ estabilizado apresentou textura moderada com apenas as componentes (023) e (032). Após a deformação de 80%, o material apresentou uma textura de fibra (001)<uvw>, pouco comum nos metais CCC, além da fibra γ (111)<uvw>, com intensidade intermediária.In this work it was studied the phenomena of work hardening, mainly phase transformation, recovery and recrystallization in the U-7.5Nb-2.5Zr alloy (Mulberry alloy) and unalloyed uranium. The alloy was melted by two methods: plasma (smaller mass) and induction (larger mass). Microstructural characterization of the samples in the as-cast and homogenized states (the last one was heat treated in the γ phase region and then quenched in water), as well as uranium in its initial state, was performed using several complementary techniques for microstructural analysis. In the gamma stabilized state, the U-7.5Nb2.5Zr alloy was deformed at room temperature by two methods: cold rolling in several stages (20%, 50%, 60% and 80%), and then filed, resulting in a powder with high degree of deformation. Deformed samples were subsequently annealed by isochronal (1 hour) and isothermal (200°C, 450°C, 700°C) treatments. Unalloyed uranium was deformed by approximately 60% and 80% reduction in thickness, and then subjected to isochronous (1 hour) and isothermal (400°C and 650°C) treatments. The phenomena of work hardening, recovery, recrystallization and phase transformation were studied by optical microscopy, hardness testing and X-ray diffraction, using the Rietveld method. Additionally, thermal analysis techniques (differential calorimetry and dilatometry) were used to measure the kinetics of phase transformation and energy stored during deformation. With regard to deformation, the U-7.5Nb-2.5Zr alloy was reduced of approximately 70% at room temperature without intermediate annealing and with a low degree of work hardening. Similarly, unalloyed uranium was reduced of high degrees of deformation at room temperature. However, this sample showed a higher degree of work hardening, and even after significant deformation still showed lots of inhomogeneities of deformation, such as deformation bands and twins. It was observed that recrystallization of unalloyed uranium started at about 454°C. For the alloy in the supersaturated and deformed states, the phase precipitation tends to occur before recrystallization. Thus, the behavior of this alloy under heat treatments after deformation can be summarized as follows: ~200°C (Recovery) ---> 300-575°C (Phase precipitation) ---> 575°C (Recrystallization). Rapid heating to temperatures above 650°C, or maintain this temperature for a long time, generates a γ recrystallized structure with equiaxed grains. Fine grain structure (~8.3 µm) was obtained for annealing at 700°C/1 h for both lower and higher deformation degrees. Slow heating rate or annealing treatment in the range of 300 to 575ºC, causes precipitation before recrystallization. Consequently, the eutectoid transformation γ→α+γ₃ occurs in order to inherit orientation from the γ deformed grain, which may generate a transformation texture. The interaction between the phenomena of phase precipitation and recrystallization was observed in the temperature range of 575-650°C. At the annealing temperature of 200°C it was possible to observe the predominance of recovery at intermediate (60%) and higher (80%) degrees of deformation, while at lower deformation degree (20%) α phase precipitation hardening has predominated. The results obtained using a differential calorimeter (DSC) showed that the energy stored during deformation and released during the recrystallization of the U-7.5Nb-2.5Zr alloy was 6.5 J/g. That value is relatively high compared to common metals, which leads to the conclusion that dislocation lines in uranium alloys possess higher energy. This fact has a direct influence in the recrystallization process. This experiment also demonstrated that the phenomena of phase precipitation and recrystallization interact with each other with regard to energy available for the process. The texture of the U-7.5Nb-2.5Zr alloy was studied by X-ray diffraction (XRD) in the γ-phase stabilized condition (obtained by melting, casting, homogenization and then quenching) and in deformed state (rolled at room temperature). The first condition generated moderate texture with the components (023) e (032). After 80% of deformation, the samples showed a fiber texture (001)<uvw>, uncommon in the BCC metals, as well the γ fiber (111)<uvw> with intermediate intensity