Synthesis and characterization of zirconia-magnesia inert matrix fuel: Uranium homolog studies

X-ray powder diffraction, X-ray fluorescence, microscopy, X-ray absorption fine structure, and electron probe microanalysis were used to characterize ZrO₂-MgO inert matrix fuel containing UO₂ (as a fissile element and a Pu homolog) and Er₂O₃ as a burnable poison. A large composition range of MgO and ZrO₂ was evaluated to determine total concentrations, local environment, phases present, phase mixing, and phase composition. It was found that most compositions of the material consist of two phases: MgO (periclase) and ZrO₂ (cubic zirconia). The zirconia phase incorporates up to 5% (wt/wt) MgO and up to 20% and 10% (wt/wt) UO₂ and Er₂O₃ respectively. This allows the fissile material and burnable poison to be incorporated into the zirconia crystal structure and defines the limits of this isomorphic substitution. The bond deformation due to the isomorphic substitution of uranium was determined by X-ray absorption fine structure. The MgO phase remains pure, which will enable design optimization of the overall thermophysical properties of the inert matrix fuel in regard to thermal diffusivity and thermal conductivity. This characterization data will be used in future studies to correlate the dissolution behavior of inert matrix material containing plutonium.     

Synthesis of zirconia sphere particles based on gelation of sodium alginate

Zirconia sphere particles were synthesized through the gelation process of Na-alginate, and cermet (ZrO₂-Mo) pellets were fabricated under several conditions. In this process, a zirconia slurry was prepared by mixing oxide powders (ZrO₂, Y₂O₃, Er₂O₃, CeO₂), distilled water and Na-alginate, and subsequently dropped into CaCl₂ solution. As a result, zirconia sphere particles coated with a gelled film were synthesized. The slurry density (zirconia content in slurry) of 30-64 wt.% and Na-alginate concentration of a few% were good for gelation for up to 10 wt.% CaCl₂ solution. Sphere particles with smaller diameter were obtained by dropping slurry with a mechanical vibration. The prolongation of the ball milling time for mixture of oxide powders was effective to increase the sintered density of zirconia sphere particles, especially for higher CeO₂ concentration. The dense cermet pellets were fabricated for max. 50% volume ratio of zirconia phase for Mo matrix using zirconia particles covered with Mo powder by a rotating granulation method.     

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.     

Fabrication of particle dispersed inert matrix fuel based on liquid phase sintered SiC

In the present work, liquid phase sintered SiC (LPS-SiC) was proposed as an inert matrix for the particle dispersed inert matrix fuel (IMF). The fuel particles containing plutonium and minor actinides were substituted with pure yttria stabilized zirconia beads. The LPS-SiC matrix was produced from the initial mixtures prepared using submicron sized α-SiC powder and oxide additives Al₂O₃, Y₂O₃ in the amount of 10 wt.% with the molar ratio 1Y₂O₃/1Al₂O₃. Powder mixtures were sintered using two sintering methods; namely conventional high temperature sintering and novel spark plasma sintering at different temperatures depending on the method applied in order to obtain dense samples. The phase reaction products were identified using X-ray diffraction (XRD) and microstructures were investigated using light microscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX) techniques. The influence of powder mixing methods, sintering temperatures, pressures applied and holding time on the density of the obtained pellets was investigated. The samples sintered by slow conventional sintering show lower relative density and more pronounced interaction between the fuel particles and matrix in comparison with those obtained with the fast spark plasma sintering method.     

MgO-pyrochlore composite as an inert matrix fuel: Neutronic and thermal characteristics

Inert matrix fuels are an important component of advanced nuclear fuel cycles, as they provide a means of utilizing plutonium and reducing the inventory of ‘minor’ actinides. We examine the neutronic and thermal characteristics of MgO-pyrochlore (A₂B₂O₇: La₂Zr₂O₇, Nd₂Zr₂O₇ and Y₂Sn₂O₇) composites as inert matrix fuels in boiling water reactors. By incorporating plutonium with resonance nuclides, such as Am, Np and Er, in the A-site of pyrochlore, the k_infvs. burn-up curves are shown to be similar to those of UO₂, although the Doppler coefficients are less negative than UO₂. The Pu depletion rates are 88-90% (²³⁹Pu) and 54-58% (total Pu) when the inert matrix fuels experience a burn-up equivalent of 45 GWd/tHM UO₂. Because of the high thermal conductivity of MgO, the center-line temperatures of the MgO-pyrochlore composites at 44.0 kW/m are lower than those of UO₂ pellets. After burn-up, the A-site cation composition is 15-35 at.% lower than that of the B-site cations in pyrochlore (e.g., A_1.84B_2.17O_7.00) due to the fission of Pu in the A-site and the presence of fission product elements in the A- and B-sites of the pyrochlore structure.     

Densification of magnesia-based inert matrix fuels using asbestos waste-derived materials as a sintering additive

A new concept for densification of minor actinide-containing inert matrix fuels (IMFs) using asbestos waste-derived materials was proposed for the effective utilization of resources and health protection of the general public. In this concept, magnesium silicates, which are mainly generated by the decomposition of asbestos in low temperature heat-treatments, are used as a sintering additive to achieve high density magnesia (MgO) -based IMFs at relatively low sintering temperature. In the present study, preliminary fabrication tests of MgO-based IMFs with magnesium silicates were carried out using cerium oxide (CeO₂) as a representative of minor actinide oxides. The sintered densities of MgO-based IMFs increased with use of the additives. The sintering behavior of MgO-based IMFs with magnesium silicate additives was discussed from the viewpoints of the effects of magnesium silicates on the densification of the MgO and CeO₂.     

Effects of swift heavy ion irradiation on the structure of Er2O3-doped CeO2

In order to simulate the effects of burnable poison doping on the fission fragment damage of UO₂ nuclear fuels, Er₂O₃-doped CeO₂ pellets were irradiated with 200 MeV Xe¹⁴⁺ ions. The irradiation effect was measured by means of X-ray diffraction (XRD). The expansion of lattice and the disordering of atomic arrangement due to the irradiation become more remarkable with increasing the concentration of the Er₂O₃ dopant.     

Gd2Zr2-xCexO7(0.0≤x≤2.0)的制备与表征

为获得钆锆烧绿石基固化体固化Pu后的物理性能、物相变化及微观形貌,本研究用Ce⁴⁺模拟Pu⁴⁺,以Gd₂O₃、ZrO₂和CeO₂粉体为原料,采用高温固相法,制备不同固溶度（0～100%,按摩尔计）的系列钆锆烧绿石固化体,并对密度、硬度、物相和微观形貌等进行表征。结果表明：实验所得系列固化体的密度和硬度均随着x的增大而增大,硬度H_V与x满足关系式H_V＝661.272 73+223.936 36x（R²＝0.946 38）。在x＝0.0时,所得固化体为单一的烧绿石结构;在x＝0.2时,固化体从烧绿石结构转变为萤石型结构;在0.2≤x≤2.0范围内,固化体均为单一萤石型结构。固化体微观形貌不规则,呈板块状。     

Melting behavior of MgO-based inert matrix fuels containing (Pu,Am)O2−x

The melting behavior of MgO-based inert matrix fuels containing (Pu,Am)O_2−x ((Pu,Am)O_2−x-MgO fuels) was experimentally investigated. Heat-treatment tests were carried out at 2173 K, 2373 K and 2573 K each. The fuel melted at about 2573 K in the eutectic reaction of the Pu-Am-Mg-O system. The (Pu,Am)O_2−x grains, MgO grains and pores grew with increasing temperature. In addition, Am-rich oxide phases were formed in the (Pu,Am)O_2−x phase by heat-treatment at high temperatures. The melting behavior was compared with behaviors of PuO_2−x-MgO and AmO_2−x-MgO fuels.     

Study on effects of swift heavy ion irradiation on the crystal structure in CeO2 doped with Gd2O3

To simulate the effects of Gd₂O₃-doping and high-energy fission products in UO₂, Gd₂O₃-doped CeO₂ pellets were irradiated with 200-MeV Xe¹⁴⁺ ions. Doping and irradiation effects were analyzed using X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS). The lattice constant of CeO₂ decreases and the local structure is disordered with increased doping levels. However, the irradiation induces an expansion of the lattice and a disordering of atomic arrangement near the Gd atoms. The effects of the irradiation become more pronounced with increasing Gd₂O₃-dopant levels. Our results are compared with those of a study involving Er₂O₃-doped CeO₂.     

Al2O3/Y2O3/ZrO2 Ceramic Composite Properties Investigation by Plasma Focus Device

The Al₂O₃–Y₂O₃–ZrO₂ eutectic composition samples were prepared using the Al₂O₃, Y₂O₃, ZrO₂ powder treated at 900 °C for 30 min, pressed at 5 ton for 15 s and sintered at 1500 °C for 2 h. The locally made dense plasma focus (DPF) system with energy 2.8 kJ was used to surface modification of these samples. The samples, mounted at distance about 2 cm from the anode, were exposed to three shots of the DPF in Ar gas at a pressure of 0.8 mbar. The phase and elemental analysis of the untreated and plasma treated samples were conducted by the Raman and EDX spectroscopy. The Raman spectroscopy showed the formation of new phases (α-Al₂O₃ and c-ZrO₂) in the treated samples. The micro-hardness of the plasma treated samples was increased by about 280 % in comparison with the untreated sample.     

A study on the burn-up characteristics of inert matrix fuels

Proper disposal of minor actinides (MA), long-lived fission products (LLFPs), and transuranium element (TRU) plays a key role in the sustainable development of fission nuclear power. Adoption of inert matrix fuels (IMFs) can effectively reduce the amount of ²³⁷Np and Np element in the spent fuel of present-day commercial power reactors. In order to study the burn-up characteristics of IMFs caused by the unique composition, burn-up calculations and MA accumulation of two typical IMFs, PuO₂ + ZrO₂ + MgO and PuO₂ + ThO₂, are performed in this paper. Results indicate that k_inf at beginning of life (BOL) and reactivity drop with burn-up for PuO₂ + ZrO₂ + MgO are much larger than those of PuO₂ + ThO₂ IMF. The yields of ²³⁷Np and Np element in IMFs are two orders smaller than those of UO₂ and mixed oxide (MOX) fuels. For the same PuO₂ volume fraction and a certain burn-up, the masses of ²³⁷Np, Np element, and ²⁴¹Am for PuO₂ + ZrO₂ + MgO are smaller than those of PuO₂ + ThO₂; however, the mass of total MA is larger. IMF has high destruction efficiencies of TRU and plutonium (Pu). The results and conclusion provide basic data for the ongoing IMF design and application study.     

High-temperature corrosion characteristics of yttria-stabilized zirconia material in molten salts of LiCl-Li2O and LiCl-Li2O-Li

The isothermal and cyclic corrosion behavior of yttria (Y₂O₃)-stabilized zirconia (ZrO₂) in a LiCl-Li₂O molten salt were investigated at 650 °C in an argon atmosphere. During isothermal and cyclic corrosion tests in the molten salt of LiCl-Li₂O for 168 h and 7 thermal cycles, the corrosion rate was very low, whereas under the molten salt of LiCl-Li₂O-Li for 168 h, the corrosion rate was almost 10 times higher than that in the molten salt of LiCl-Li₂O. No corrosion product was detected until 168 h for the isothermal corrosion test, however, after 7 thermal cycles, a very-low-intensity Li₂ZrO₃ peak was detected at the beginning stage of the chemical reaction between ZrO₂ and Li₂O. Additionally, in the molten salt of LiCl-Li₂O-Li for 168 h, a large amount of Li₂ZrO₃ was formed, with evidence of marked cracks, pores, and spallations on the corroded surface. The introduction of Y₂O₃-stabilized ZrO₂ was beneficial in increasing the hot corrosion resistance of the structural materials used to handle molten salts containing Li₂O at elevated temperature without forming a lithium at the cathode during the electrolytic reduction process.     

Laser Graving of Characters on Ceramic Substrates and Change in Visibility in Corrosive Environments

Laser graving of lines and characters was studied on alumina (Al₂O₃), zirconia (ZrO₂) and silicon carbide (SiC) substrates to apply it to prolonged record conservation media. Graved lines were not clear on alumina and zirconia substrates, whereas on a SiC board, they were clearly identified by optical observation. Characters were graved on SiC substrates, and the stability of their visibility was investigated by thermal and chemical corrosion examinations. In high-temperature corrosion examination of the graved SiC, the visibility of characters decreased after 1 week, but no more changes were subsequently observed. In chemical corrosion examination, the visibility was remarkably degraded in concentrated alkaline solution, but not changed in acid and diluted alkaline solutions.     

Ion-induced amorphization in ceramic materials

Amorphization induced by swift heavy ions is discussed, the main features are reviewed and explained by the author’s model. In Al₂O₃ and MgAl₂O₄ the recrystallization reduces considerably the track diameters. The threshold electronic stopping power for amorphization S_et can be estimated reliably for these solids from the position of the amorphous-crystalline boundary formed at high ion fluences. The results are in good agreement with the predictions of the model. Experiments on CeO₂ and UO₂ are discussed. Estimates of S_et are made for β-Si₃N₄, CeO₂, pure ZrO₂, ZrSiO₄, and UO₂, and 10.1 > S_et > 6.2 keV/nm is obtained at room temperature for fission fragment energies. At about 1000 °C operation temperature, S_et is reduced by about 35-50%. No amorphization is expected by ion bombardment in AlN, SiC (semiconductors) and MgO (ionic crystal).     

Metallurgical characterizations of Fe–Cr–Ni–Zr base alloys developed for geological disposal of radioactive hulls

Alloy melting route is currently being considered for radioactive hulls immobilization. Towards this, wide range of alloys, belonging to Zirconium–Iron binary and Zirconium–Stainless steel pseudo-binary systems have been prepared through vacuum arc melting route. Detail microstructural characterization and quantitative phase analyses of these alloys along with interaction study between Zirconium and Stainless steel coupons at elevated temperatures identify Zr(Fe,Cr)₂, Zr(Fe,Cr), Zr₂(Fe,Cr), Zr₃(Fe,Ni), Zr₃(Fe,Cr), Zr₃(Fe,Cr,Ni), β-Zr and α-Zr as the most commonly occurring phases within the system for Zirconium rich bulk compositions. Nano-indentation studies found Zr(Fe,Cr)₂ and Zr(Fe,Cr) as extremely hard, Zr₃(Fe,Ni) as moderately ductile and β-Zr, Zr₂(Fe,Cr) as most ductile ones among the phases present. Steam oxidation studies of the alloys, based on weight gain/loss procedure and microstructural characterization of the mixed oxide layers, suggest that each of the alloys responded to the corrosive environment differently. Fe₂O₃, NiFe₂O₄, NiO, monoclinic ZrO₂ and tetragonal ZrO₂ are found to be most common constituents of the oxide layers developed on the alloys. Integrating the microstructural, mechanical and corrosion properties, ZrFeCrNi3 (Zr: 84.00, Fe: 11.20, Cr: 3.20, Ni: 1.60, in wt.%) is identified as the acceptable base alloy for disposal of radioactive hulls.     

Thermal and mechanical properties of (U,Er)O2

Erbium is considered as a slow burnable poison suitable for use in light water reactors (LWRs). Addition of a small amount of Er₂O₃ to all UO₂ pellets will make it possible to develop super high burnup fuels in Japanese nuclear facilities which are now under the restriction of the upper limit of ²³⁵U enrichment. When utilizing the (U,Er)O₂ fuels, it is very important to understand the thermal and mechanical properties. Here we show the characterization results of (U_1−xEr_x)O₂ (0 ? x ? 0.1). We measured their thermal and mechanical properties and investigated the effect of Er addition on these properties of (U,Er)O₂. All Er completely dissolved in UO₂, and the lattice parameter decreased linearly with the Er content. Both the thermal conductivity and Young’s modulus of (U,Er)O₂ decreased with the Er content. These results would be useful for us in evaluating the performance of the (U,Er)O₂ fuels in LWRs.     

Characterisation of an oxygen sensor based on In/In2O3 reference electrode

A potentiometric sensor for measuring oxygen activity in LBE has been developed since 2000 until today at ‘Institut Quimic de Sarria’ electrochemistry laboratories. This sensor is based on In/In₂O₃ reference electrode. The last experiments performed with this sensor have been directed to characterise the sensor. For this purpose, the following experiments in stagnant conditions have been performed: effect of the operating temperature from 300 to 500 °C, different covering gases (N₂ + 5% H₂, Ar 99.999%, and N₂ + 10 mg/L O₂) and comparison of different solid electrolytes (ZrO₂/Y₂O₃ and ZrO₂/MgO). Long-term experiments have also been performed to the see the stability of the signal with time.     

Fabrication and characterization of silicon nitride-based inert matrix fuels sintered with magnesium silicates

The effects of sintering additives of magnesium silicates, i.e. enstatite (MgSiO₃), steatite (MgSiO₃) and forsterite (Mg₂SiO₄), on the sintering behaviors and characteristics of the silicon nitride ceramics-based inert matrix fuels (IMFs) were experimentally investigated. Fabrication tests and characterizations of Si₃N₄-based IMFs with the sintering additives were carried out using cerium oxide (CeO₂) to represent minor actinide oxides. Sintered bodies were characterized in terms of their densities and thermal conductivities. In addition, a solubility test with hot nitric acid was carried out for evaluation of applicability to the existing reprocessing technology. The densification of sintered bodies was enhanced by using additives of magnesium silicates at relatively low sintering temperature. In particular, the relative density of Si₃N₄-based IMFs with Mg₂SiO₄ was above 90% at 1723 K. The thermal conductivities of Si₃N₄-based IMFs varied according to sintering temperature, and for the IMFs sintered at 1923 K were above 34 W/m K. The solubility test results revealed that only grain boundary phases in Si₃N₄-based IMFs can be dissolved into hot nitric acid.