Oxidation and hydrolysis of thorium doped uranium nitride fuel for use in LWR

Uranium nitride is being investigated as a replacement for UO2 as it shows enhanced thermal properties and seems to be a promising accident tolerant fuel (ATF) candidate. The main drawback of UN fuel is its innate low oxidation resistance in air/water environments. This becomes a challenge for the implementation of UN fuel in water-cooled reactors. The effect of thorium doping in the stability of uranium nitride microspheres and pellets sintered by spark plasma sintering (SPS) was investigated in oxidizing environments using thermogravimetric analysis and autoclave testing. It was found that during oxidation in air the density had a noticeable effect, increasing the reaction onset temperatures in pellets with higher densities. In addition, thorium doping improved the oxidation resistance of pellets in air by increasing the maximal reaction rate temperature by approximately 50 K. However, this effect was almost nonexistent in highly porous doped microspheres. The interaction with water at 373 K showed that pellets manufactured using SPS can survive unchanged for at least six hours in boiling water, which is an improvement to cold-pressed pellets. At 473 and 573 K, the pellets were oxidized and disintegration into an oxide powder was observed. Thorium-doped uranium nitride pellets did not present any improvement with respect to the oxidation resistance of UN in water at these temperatures

Scoping Studies of Dopants for Stabilization of Uranium Nitride Fuel

Uranium nitride (UN) is considered as nuclear reactor fuel because of, among other reasons, its high uranium density and its high thermal conductivity. Its main drawback is that it relatively easily dissolves in hot water, which is particularly problematic when it is used in water-cooled reactors. One possible remedy to this is to add some corrosion inhibitor as dopant to the UN matrix. A number of dopants have been identified that have the potential to inhibit the dissolution process, and their respective merits have been investigated both by neutronic simulations and dissolution experiments. It is concluded that chromium is the most promising candidate

Preparation of Chromium doped uranium nitride via Sol-Gel and Carbothermic reduction

Uranium nitride (UN) has been proposed as an accident tolerant fuel due to its enhanced thermal properties compared to the standard UO2. However, due to its low oxidation resistance, its implementation in water cooled reactors has not been allowed. A method to improve the corrosion resistance involves doping with oxide scale forming elements such as aluminum or chromium. In this work, UN microspheres were produced by an internal gelation method followed by carbothermic reduction and nitridation. Chromium was added as dopant in the solution to produce a homogenous mixture with uranium. The ternary phase (U2CrN3) was observed for the first time in Cr-doped UN microspheres produced via sol-gel and carbothermic reduction. Materials with and without the ternary phase were produced, and a mechanism of reaction was proposed. Chromium precipitations were also observed on the surface of the microspheres produced, indicating low solubility of Cr compounds in the UN matrix. ICP-MS and XRF measurements showed that Cr content is reduced after heating treatments, probably due to evaporation. Additionally, these results showed that Cr in the ternary phase is completely soluble in aqua regia, unlike the Cr in the material without the ternary phase

Application of SPS in the fabrication of UN and (U,Th)N pellets from microspheres

In this study, the process involved in the fabrication of a potential accident tolerant fuel is described. Homogeneous uranium nitride microspheres doped with different thorium content were successfully manufactured using an internal gelation process followed by carbothermic reduction, and nitridation. Elemental analysis of the materials showed low carbon and oxygen content, the two major impurities found in the products of carbothermic reduction. Uranium nitride microspheres were pressed and sintered using spark plasma sintering (SPS) to produce pellets with variable density. Final density can be tailored by choosing the sintering temperature, pressure and time. Density values of 77–98% of theoretical density (%TD) were found. As expected, higher temperatures and pressures resulted in a denser material. Furthermore, a direct correlation between the onset sintering temperature and thorium content in the materials was observed. The change of onset temperature has been related to an increment in the activation energy for self-diffusion due to the substitution of uranium atoms by thorium in the crystal structure

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

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

Nitride fuel for Gen IV nuclear power systems

Nuclear energy has been a part of the energy mix in many countries for decades. Today in principle all power producing reactors use the same techniqe. Either PWR or BWR fuelled with oxide fuels. This choice of fuel is not self evident and today there are suggestions to change to fuels which may be safer and more economical and also used in e.g. Gen IV nuclear power systems. One such fuel type is the nitrides. The nitrides have a better thermal conductivity than the oxides and a similar melting point and are thus have larger safety margins to melting during operation. In addition they are between 30 and 40% more dense with respect to fissile material. Drawbacks include instability with respect to water and a sometimes complicated fabrication route. The former is not really an issue with Gen IV systems but for use in the present fleet. In this paper we discuss both production and recycling potential of nitride fuels

3D video quality of experience - influence of scale and crosstalk

This paper gives an overview of three recent studies by the authors on the topic of 3D video Quality of Experience (QoE). Two of studies [1,2] investigated different psychological dimension that may be needed for describing 3D video QoE and the third the visibility and annoyance of crosstalk[3]. The results shows that the video quality scale could be sufficient for evaluating S3D video experience for coding and spatial resolution reduction distortions. It was also confirmed that with a more complex mixture of degradations more than one scale should be used to capture the QoE in these cases. The study found a linear relationship between the perceived crosstalk and the amount of crosstalk

Management learning at the speed of life:Designing reflective, creative, and collaborative spaces for millenials

This paper introduces the concept of "management learning at the speed of life" as a metaphor to inspire millenials. Millenials may face three major problems in relation to management learning: lack of concentration, lack of engagement, and lack of socialization. Management learning at the speed of life addresses these potential problems through three dimensions: reflective, creative, and collaborative learning. This paper illustrates the benefits of reflective, creative, and collaborative spaces for millenials using practices from leadership and personal development courses that were offered over seven years in Canada, Turkey, and the UK. These courses incorporated the latest technology that brought the course activities up to the speed of life