TEM investigations of MN nitride phases in a 9% chromium ferritic/martensitic steel with normalization conditions for nuclear reactors

The investigations on the precipitate phases in a 9%Cr ferritic/martensitic steel under different normalization conditions have been made by using a transmission electron microscope and an energy-dispersive X-ray spectroscopy. Hot-rolled steel samples were normalized at 1050-1200 °C for 1-2 h followed by an air cooling to room temperature. MN vanadium nitride precipitates with a plate-like morphology and a chemical formula of about (V_0.4Nb_0.4Cr_0.2)N have been observed at triple junctions, grain boundaries and within matrix in the steel samples normalized at 1050-1150 °C for 1-2 h, but they were dissolved out at 1200 °C within 1 h. Vanadium nitride is a stable phase at 1050 °C according to thermocalc prediction of equilibrium phases in the steel. With increasing normalizing temperature and time, there was no a striking change in the chemical composition of metallic elements in the MN phase, but a considerable increase in the size of the MN precipitate.     

Vanadium nitride precipitate phase in a 9% chromium steel for nuclear power plant applications

Vanadium nitride precipitate phase in a 9% Cr steel was observed and analyzed using transmission electron microscopy and energy dispersive spectroscopy. The steel samples were normalized at 1050 and 1100 °C for 1 h and then tempered at 750 °C for 30 min to 5 h followed by an air cooling. Through the microdiffraction pattern analyses and energy dispersive X-ray data, two kinds of vanadium nitride precipitates were determined to be (V_0.6Nb_0.2Cr_0.2)N and (V_0.45Nb_0.45Cr_0.1)N with the same fcc crystal structure and different lattice parameters ā = 4.070 and 4.232 Å, respectively. Lattice parameters estimated for the precipitates regarding the VN phase agree well with the present data from the microdiffraction patterns, indicating that the precipitates do not belong to the VC phase. Observed (V_0.45Nb_0.45Cr_0.1)N precipitates consisted of undissolved particles remaining after a normalizing and the particles newly precipitated during a tempering, whilst, the observed (V_0.6Nb_0.2Cr_0.2)N precipitates were formed during a tempering. These two vanadium nitrides seem to be a stable phase, and not an intermediary phase.     

The effect of processing on the thermal diffusivity of MgO-Nd2Zr2O7 composites for inert matrix materials

Oxides possess many of the required properties suitable for an inert matrix fuel in light water reactors, however, their primary disadvantage is low thermal conductivity. Composites are being investigated to maximize the thermal conductivity of the inert matrix fuel by using thermally conductive MgO as the primary phase while improving its hot water corrosion resistance through the addition of a second phase acting as a hydration barrier. Inert matrix fuel candidate MgO-Nd₂Zr₂O₇ composites were synthesized with multiple processing methods, the composite powders were characterized, the resulting microstructures quantitatively analyzed, and the thermal diffusivity of the composites was measured. Among the four processing methods investigated, ball milling and high-energy shaker blending produced the most homogeneous microstructures with a negligible amount of MgO and Nd₂Zr₂O₇ heterogeneities. An effect of processing on the properties of the composites manifests as a larger variation in the thermal diffusivity in pellets processed by methods that produce a higher quantity and frequency of MgO and Nd₂Zr₂O₇ heterogeneities than in methods that produce negligible amounts of heterogeneities.     

Investigation on boron carbide oxidation for nuclear reactor safety: Experiments in highly oxidising conditions

The oxidation kinetics of boron carbide pellets were investigated in steam/argon mixtures in the temperature range 1200-1800 °C for steam partial pressures between 0.2 and 0.8 bar and total flows (steam + argon) between 2.5 and 10 g/min resulting in gas velocities from 1.01 to 5.34 m/s. A kinetic model for boron carbide pellet oxidation depending on temperature, steam partial pressure and flow velocity is obtained. The activation energy of the oxidation process was determined to be 163 ± 8 kJ/mol. The strong influence of temperature and steam partial pressure on the boron carbide oxidation kinetics is confirmed. The obtained data suggest the coexistence of two kinetic regimes, one at 1200 °C and the other at 1400-1800 °C, with different dependence on steam partial pressure.     

Synthesis of dysprosium and cerium nitrides by a mechanically induced gas-solid reaction

A high energy ball milling process was used to produce dysprosium nitride and cerium nitride powders at room temperature. Dysprosium and cerium metal flakes were milled in a 275 kPa nitrogen atmosphere for 24 h at ambient temperatures. X-ray diffraction confirmed the formation of phase pure dysprosium nitride and cerium nitride powders. The median particle size of the resultant dysprosium nitride was measured as 4 μm using a laser scattering technique. The particle size of the cerium nitride was not measured due to its reactive nature.     

Investigation of passive films on nickel Alloy 690 in lead-containing environments

Passive films formed on Alloy UNS N06690 were investigated in simulated crevice chemistries. It was found the role of lead in corrosion processes is strongly dependent on the pH value of the testing solutions. At pH 1.5 the effect of lead is narrowly noticeable; while at pH 12.7, lead has a significant influence on the electrochemical performance of alloy UNS N06690. The lead alters the surface morphologies at both pH and account for higher hydroxide content in the surface film at pH 12.7. The lead incorporation hinders the formation of spinel oxides during the passivation in alkaline solution. Nanoindentation tests indicate a significant lead-induced degradation in the mechanical properties of passive films. The passivation degradation is attributed to detrimental effects of lead via interrupting the dehydration process and hindering the formation of protective layers on the alloy surface.     

Fabrication method for UO2 pellets with large grains or a single grain by sintering in air

The effects of a powder treatment, the sintering temperature and the sintering time on the grain growth of UO₂ pellets were investigated in air to obtain UO₂ pellets with large grains. Air could be used for sintering because an oxidation path above 1803 K does not pass through a two-phase (UO_2+x + U₃O_8−z) region. The UO₂ pellets sintered by the CO₂-air-CO₂-H₂ process consisted of a single grain or some large grains in the order of several millimeters.     

Crystal structure and magnetic properties of UFe5Ga7

The new ternary compound UFe₅Ga₇ was prepared by an argon arc-melting followed by annealing. This intermetallic compound belongs to the series UFe_xGa_12−x and crystallizes in a structure related with the ThMn₁₂-type, with a = 8.6309 Å and c = 5.0524 Å. EDS elemental analysis yielded the phase composition UFe_4.9(2)Ga_6.8(1), which is very close to the nominal composition. Dc magnetization measurements revealed ferromagnetic type of magnetic ordering in UFe₅Ga₇. The Curie temperature of ∼439 K was estimated by the temperature dependence of magnetization at a low magnetic field of 0.1 T.     

Fabrication of uniform ZrC coating layer for the coated fuel particle of the very high temperature reactor

Fuel for the very high temperature reactor is required to be used under severer irradiation conditions and higher operational reactor temperatures than those of present high temperature gas cooled reactors. Japan Atomic Energy Agency has developed zirconium carbide (ZrC)-coated fuel particles previously in laboratory scale which are expected to maintain their integrity at higher temperatures and burnup conditions than conventional silicon carbide-coated fuel particles. As one of the important R&D items, ZrC coating process development has been started in the year 2004 to determine the coating conditions to fabricate uniform structure of ZrC layers by using a new large-scale coater up to 0.2 kg batch. It was thought that excess carbon formed in the ZrC layer under the oscillation of coating temperature would cause non-uniformity of the ZrC layer. Finally, uniform ZrC coating layer has been fabricated successfully by adjusting the time constant of the coater and keeping the coating temperature at around 1400 °C.     

Development of oxides dispersion strengthened steels for high temperature nuclear reactor applications

By introducing a dispersion of nanosized yttrium oxides particles into a steel matrix, the upper temperature limit in mechanical creep strength can be enhanced in temperature by 100 K at least. Production routes for the production of a new class of oxides dispersion strengthened (ODS) steels are investigated within this work. Preliminary results obtained when doping pure iron matrix phase with two types of yttrium oxides (Y₂O₃) nanoparticles (commercial as well as laboratory fabricated nanopowder) are presented. The twofold purpose of this work is firstly to obtain a comparative analysis between the commercial and the laboratory fabricated Y₂O₃ nanopowder used to produce the doped iron, and secondly to demonstrate the feasibility of new production route by observing the nanostructure of the first test batches with pure iron. Observations are carried out with transmission electron microscopy (TEM) to determine the size distribution of the particles in the powder, while glow discharge optical emission spectroscopy (GDOES) and high resolution-scanning electron microscopy (HR-SEM) are used to analyze the chemical composition and the homogeneity of the produced doped iron. It is demonstrated, that even with small size particles nanopowder fabricated in the laboratory, the distribution is fairly homogeneous compared to the one obtained with a relatively large particles commercial nanopowder, confirming the feasibility of the new production route.     

Kinetics of precipitation of U4O9 from hyperstoichiometric UO2+x

For safe and reliable operation of fission reactors in space, the phase diagrams and reaction kinetics of systems used as nuclear fuels, such as U-O, U-N, U-C, are required. Diffraction allows identification of phases and their weight fractions as a function of temperature in situ, with a time resolution of the order of minutes. In this paper, we will provide results from a neutron diffraction experiment studying the U-O system. Using the neutron diffractometer HIPPO, the decomposition of UO_2+x into UO₂ and U₄O₉ as a function of temperature was investigated in situ. From the diffraction data, the participating phases could be identified as UO_2+x, UO₂ and U₄O_8.94 and no stoichiometric U₄O₉ was found. Results of the experiment were used to improve existing thermodynamic models. The presented techniques (i.e., neutron diffraction and thermodynamic modeling) are also applicable to the other systems mentioned above.     

Thermal expansion of TRU nitride solid solutions as fuel materials for transmutation of minor actinides

The lattice thermal expansion of the transuranium nitride solid solutions was measured to investigate the composition dependence. The single-phase solid solution samples of (Np_0.55Am_0.45)N, (Pu_0.59Am_0.41)N, (Np_0.21Pu_0.52Am_0.22Cm_0.05)N and (Pu_0.21Am_0.18Zr_0.61)N were prepared by carbothermic nitridation of the respective transuranium dioxides and nitridation of Zr metal through hydride. The lattice parameters were measured by the high temperature X-ray diffraction method from room temperature up to 1478 K. The linear thermal expansion of each sample was determined as a function of temperature. The average thermal expansion coefficients over the temperature range of 293-1273 K for the solid solution samples were 10.1, 11.5, 10.8 and 8.8 × 10⁻⁶ K⁻¹, respectively. Comparison of these values with those for the constituent nitrides showed that the average thermal expansion coefficients of the solid solution samples could be approximated by the linear mixture rule within the error of 2-3%.     

Influence of different chemical elements on irradiation-induced hardening embrittlement of RPV steels

Fe–Cu binary alloys are often used to mimic the behaviour of reactor pressure vessel steels. Their study allows identifying some of the defects responsible for irradiation-induced hardening. But recently the influence of manganese and nickel in low-Cu steels has been found to be important as well. In contrast with existing models found in the literature, which predict that hardening saturates after a certain dose, Fe alloys containing nickel and manganese irradiated in a material test reactor (BR2) show a continuous increase of hardening, up to doses equivalent to about 40 years of operation. Considerations based on positron annihilation spectroscopy analyses suggest that the main objects causing hardening in Cu-free alloys are most probably self-interstitial clusters decorated with manganese. In low-Cu reactor pressure vessel steels and in Fe–CuMnNi alloys, the main effect is still due to Cu-rich precipitates at low doses, but the role of manganese-related features becomes predominant at higher doses.     

Potential application of Laser Solid Forming Technology for fabrication of breeding blanket

To solve the fabrication of breeding blanket with complex structure, LSF (Laser Solid Forming) as a novel technology is proposed. The fabrication process of U-shaped first wall (one of components in breeding blanket) by LSF was shown. To verify the feasibility of LSF being applied in fabrication of breeding blanket, experiments based on CLF-1 (one of Reduced Activation Ferritic/Martensitic (RAFM) steels) by LSF (which is assigned as LSFed CLF-1 in this paper) is performed. The preliminary results show that main chemical composition is almost not changed from forgings of CLF-1 to LSFed CLF-1. As-deposited LSFed CLF-1 has high tensile strength, anisotropy and low ductility. However LSFed CLF-1 after proper heat-treatment can achieve homogenized structure, fully martensite phase, better tensile strength (ultimate tensile strength is 848 MPa) and comparable ductility (elongation is 17.3%), which suggests the possibility that LSF can be applied in fabrication of breeding blanket.     

Synthesis of uranium nitride by a mechanically induced gas-solid reaction

A high energy, low-temperature, ball-milling route was used to directly produce uranium nitride. Pure uranium metal particles (∼100 μm) were ball milled under a 420 kPa nitrogen atmosphere for 24 h at ambient temperature to yield phase pure U₂N₃ powder as confirmed by X-ray diffraction and energy dispersive spectroscopy. The median particle size was measured to be approximately 6 μm.     

Effect of sintering conditions on the microstructure and mechanical properties of ZrN as a surrogate for actinide nitride fuels

Pellets of sintered ZrN were studied to optimize the mechanical properties and microstructures needed in nitride fuel pellets, using ZrN as a surrogate for actinide nitrides and as potential component in low fertile and inert matrix fuels. Samples were prepared via sintering in either Ar or N₂ (with and without 6% H₂) and at 1300 °C or 1600 °C. A significant difference in the hardness was measured ranging from 1000 (Kg/mm²) in samples sintered at 1600 °C in argon to 100 (Kg/mm²) in samples sintered at 1300 °C in nitrogen. Samples with 6% hydrogen added to the sintering environment experienced a decrease in hardness, as well as an increase in intergranular cracking as compared to samples sintered without hydrogen, suggesting hydrogen embrittlement. Grain size was more uniform in samples sintered in pure Ar as compared to Ar-H₂, while the latter had a larger fraction of high angle grain boundaries than the former. Cracking around indents had a clear tendency to follow high angle boundaries, which were found to be intrinsically weak in ZrN.     

Structural study of the oxidation process and stability of NbOxNy coatings

In the present work, we study the oxidation behaviour of NbON multilayer films. The films were deposited by DC magnetron sputtering with a reactive gas pulsing process. The nitrogen flow was kept constant and the oxygen flow was pulsed. Pulse durations of 10 s produced multilayered coatings with a period of λ = 10 nm. Three different films with increasing duty cycles have been deposited.Rutherford backscattering spectroscopy (RBS) was used to study the chemical composition variations at different annealing temperatures (as-deposited, 400 °C, 500 °C and 600 °C) combined with X-ray diffraction (XRD) to identify the crystalline phases formed. At 400 °C, for all films a very thin layer starts to form at the surface with enhanced O concentration. The composition of the deeper part of the samples remains unchanged. At 500 °C, the oxide scale grows, encompassing about half the film thickness. At 600 °C, the process is finished and a single layer is formed with reduced Nb and increased O concentration. Fourier-transformation infrared spectroscopy (FTIR) results confirmed the increase of this surface oxidation, while XRD revealed that crystallization of Nb₂O₅ occurs at 600 °C.     

Damage of actively cooled plasma facing components of magnetic confinement controlled fusion machines

Plasma facing components (PFCs) of magnetic fusion machines have high manufactured residual stresses and have to withstand important stress ranges during operation. These actively cooled PFCs have a carbon fibre composite (CFC) armour and a copper alloy heat sink. Cracks mainly appear in the CFC near the composite/copper interface. In order to analyse damage mechanisms, it is important to well simulate the damage mechanisms both of the CFC and the CFC/Cu interface. This study focuses on the mechanical behaviour of the N11 material for which the scalar ONERA damage model was used. The damage parameters of this model were identified by similarity to a neighbour material, which was extensively analysed, according to the few characterization test results available for the N11. The finite elements calculations predict a high level of damage of the CFC at the interface zone explaining the encountered difficulties in the PFCs fabrication. These results suggest that the damage state of the CFC cells is correlated with a conductivity decrease to explain the temperature increase of the armour surface under fatigue heat load.     

Precipitate phases of a ferritic/martensitic 9% Cr steel for nuclear power reactors

One of the reasons that ferritic/martenstic steels have been considered as candidate materials for nuclear power reactors is their superior creep resistance at elevated temperature. The creep rupture strength of 9% chromium steel could be improved by a fine dispersion of secondary precipitate phase. The precipitate phases in extra-low carbon 9% chromium steel with tempered conditions were investigated by transmission electron microscope and energy-dispersive X-ray analysis. The steel specimens were normalized and then tempered at different temperatures. Niobium-rich MN nitrides (Nb_0.6V_0.3Cr_0.1)N, and two kinds of vanadium nitrides, (V_0.6Nb_0.2Cr_0.2)N and (V_0.45Nb_0.45Cr_0.1)N having a f.c.c. crystal structure, were identified in the steel specimens tempered at 600-780 °C, and 750 or 780 °C respectively. Hexagonal chromium-rich M₂N precipitate phases with different lattice parameters, a = 2.80 Å/c = 4.45 Å and a = 7.76 Å/c = 4.438 Å, were determined in the tempered steel specimens. The M₂N phase showed a decrease/an increase in its chromium/vanadium content as the tempering temperature was increased. The influence of precipitates and heat treatment conditions on the high temperature properties of 9% Cr steel was discussed.     

Preparation, sintering and leaching of optimized uranium thorium dioxides

Mixed actinide dioxides are currently studied as potential fuels for several concepts associated to the fourth generation of nuclear reactors. These solids are generally obtained through dry chemistry processes from powder mixtures but could present some heterogeneity in the distribution of the cations in the solid. In this context, wet chemistry methods were set up for the preparation of U_1−xTh_xO₂ solid solutions as model compounds for advanced dioxide fuels. Two chemical routes of preparation, involving the precipitation of crystallized precursor, were investigated: on the one hand, a mixture of acidic solutions containing cations and oxalic acid was introduced in an open vessel, leading to a poorly-crystallized precipitate. On the other hand, the starting mixture was placed in an acid digestion bomb then set in an oven in order to reach hydrothermal conditions. By this way, small single-crystals were obtained then characterized by several techniques including XRD and SEM. The great differences in terms of morphology and crystallization state of the samples were correlated to an important variation of the specific surface area of the oxides prepared after heating, then the microstructure of the sintered pellets prepared at high temperature. Preliminary leaching tests were finally undertaken in dynamic conditions (i.e. with high renewal of the leachate) in order to evaluate the influence of the sample morphology on the chemical durability of the final cohesive materials.