γ辐照联合H_2O_2处理污泥滤液的研究

采用60 Coγ射线辐照处理污泥滤液,通过对比处理前后化学需氧量(COD)、紫外可见吸光度和浑浊度的变化,研究了辐照处理中初始pH、初始H2O2浓度和吸收剂量对污泥滤液处理效果的影响。结果表明:在相同吸收剂量和初始H2O2浓度条件下,酸性条件更利于CODCr的降低;γ辐照联合H2O2处理存在显著协同效应,吸收剂量为18.75kGy、初始H2O2浓度为2mmol/L时,污泥滤液CODcr去除率达70.4%,浑浊度下降94.9%。     

Evolution of the oxide structure of 9CrODS steel exposed to supercritical water

The corrosion behavior and oxide structure of 9CrODS steel in supercritical water has been studied. Samples were exposed to supercritical water at 500 and 600 °C for times of 2, 4 and 6 weeks. The oxide structure was studied using microbeam synchrotron X-ray diffraction and fluorescence analysis. The 600 °C samples exhibited a three-layer structure with Fe₃O₄ in the outer layer, a mixture of FeCr₂O₄ and Fe₃O₄ in the inner layer, and a mixture of metal and oxide grains (FeCr₂O₄ and Cr₂O₃) in the diffusion layer. Between the 2 and 4-week samples exposed to 600 °C supercritical water, a Cr₂O₃ film appeared at the diffusion layer-metal interface which appears to be associated with slower oxidation of the metal. The 500 °C samples also showed a three-layer structure, but both the outer and inner oxide layers contained mainly Fe₃O₄, and the diffusion layer contained much fewer oxide precipitates and was a solid solution of oxygen ahead of the oxide front.     

Ion beam analysis of partial lithium extraction of LiMn2O4 by chemical delithiation

Lithium manganese oxide, LiMn₂O₄, has been studied by many research groups. This material is a great candidate to be used as positive electrode in rechargeable lithium-ion batteries because of its low cost, abundant precursors and non-toxicity. LiMn₂O₄ has a spinel Fd-3m structure and shows a reversible extraction and insertion of lithium ions that is one of the most important characteristic of positive electrodes in rechargeable batteries.In this work, LiMn₂O₄ samples were synthesized by solid state reaction. A partial lithium removal was performed on this system by chemical delithiation using HCl aqueous solutions at different concentrations. Six partial-extracted compounds were obtained and characterized by Ion beam analysis (IBA) in order to obtain the Li concentrations. X-ray diffraction (XRD) and Rietveld analyses were also performed. A rigorous study of lithium contents is critical to analyze the structure properties of these compounds and samples production parameters. The IBA method used in this work was the analysis of energy spectra of elastic backscattered (EBS) proton from Mn, O and Li nuclei and the α-particles energy from the ⁷Li(p,α)⁴He nuclear reaction (NR).     

Characterization of oxide films formed on alloy 182 in simulated PWR primary water

The oxide film, formed on the alloy 182 due to the exposure to simulated Pressurized Water Reactor primary water conditions, is characterized using X-ray Photoelectron Spectroscopy, Scanning Electron Microscopy and Raman spectroscopy. As a consequence of the low redox potential for nickel, loosely bound oxide film consisting mainly of chromium oxide, is formed on the surface of the alloy. The oxide film is found to have a double-layer structure, with an inner layer rich in Cr₂O₃, outer layer rich in FeCr₂O₄. Thin Ni(OH)₂ and Fe₃O₄ clusters were observed on top of the oxide film. The morphology and thickness of the layers critically depend on the exposure times and surface treatments prior to the exposure.     

Magnetic Measurements of NiFe2O4 Formation from Iron Hydroxides and Oxide in High Temperature Water

Formation of NiFe₂O₄ from iron hydroxides and an oxide has been studied in high temperature water by in situ measurements. The five kinds of Fe compounds used in the experiments are known as components of Fe crud in BWR condensate water. Among the reactants and products, only NiFe₂O₄ shows ferromagnetism. An in situ method, using a magnetic balance, was developed to measure the mass of NiFe₂O₄ in high temperature water. The lower detection limit of this method is 0.01 mg of NiFe₂O₄ with a maximum detection error of ±2%. The iron hydroxides react with Ni(OH)₂ to form NiFe₂O₄ and α-Fe₂O₃ through a dehydration reaction in 553 K water. Amorphous iron hydroxide and γ-FeOOH react rapidly, reaching saturated values of the conversion to NiFe₂O₄ within a few hours at 553 K. The dissolved oxygen has no influence on the NiFe₂O₄ formation. The amount of generated NiFe₂O₄ decreases with the reduction of the pH value, due to dissolution of the reactant. The rate of NiFe₂O₄ formation increases with reaction temperature, while the saturated value of formed NiFe₂O₄ decreases.     

Transmission electron microscopy of oxide development on 9Cr ODS steel in supercritical water

Oxide layers formed on 9Cr oxide dispersion strengthened ferritic steel alloys during exposure to 600 °C supercritical water for 2- and 4-weeks were examined using cross-sectional transmission electron microscopy. A focused ion beam insitu lift-out technique was used to produce site-specific samples with electron transparent areas up to 8 μm by 10 μm. The oxide layers consist of several sub-layers: an Fe-rich outer oxide, a Cr-rich inner oxide, and a diffusion layer, extending beyond the oxide front into the metal. An evolution of the oxide layer structure is seen between 2 and 4 weeks, resulting in the development of a band of Cr₂O₃ at the diffusion layer/metal interface from the previously existing continuous mixture of FeCr₂O₄ ‘fingers’ and bcc metal. It is believed that transport in this Cr₂O₃ layer at the diffusion layer/metal interface becomes the rate-limiting step for oxide advancement, since this change in oxide structure also corresponds to a decrease in corrosion rate.     

Application of combined neutron diffraction and impedance spectroscopy for in-situ structure and conductivity studies of La2Mo2O9

In-situ neutron diffraction combined with AC impedance spectroscopy was applied successfully to investigate the correlation between crystal structure and electrical properties of the La₂Mo₂O₉ oxide ion conducting electrolyte material. Neutron diffraction patterns were collected as a function of temperature while the AC impedance spectra were recorded simultaneously using a modified sample environment to monitor the conductivity change of the sample. A close relationship between unit cell parameters and the bulk conductivity was observed, confirming that the oxygen transport is dependent on the lattice structure. With the transition from the low temperature alpha to the high temperature beta phase, expansion of the crystal structure makes more space available for oxygen transport, leading to a dramatic increase of the ionic conductivity. The successful application of this technique provides a new method to simultaneously investigate crystal structure and electrical properties in electro-ceramics in the future.     

Recovery of neutron-irradiation-induced defects of Al2O3, Y2O3, and yttrium-aluminum garnet

SiC fiber-reinforced SiC matrix composites (SiC_f/SiC) are considered as one of the candidates for blanket materials in future fusion reactors and as an advanced fuel cladding material for next-generation fission reactors. Generally, the densification of SiC needs sintering additives and oxides such as Al₂O₃, Y₂O₃, and yttrium-aluminum garnet (YAG, Y₃Al₅O₁₂), which are frequently added to SiC. However, the effects of neutron irradiation on sintering additives are still unclear. In this study, we performed the neutron irradiation of Al₂O₃, Y₂O₃, and YAG at fluences up to 2.0–2.5 × 10²⁴ n/m² (E > 0.1 MeV) at 60–90 °C. The isochronal recovery of the macroscopic volume of Al₂O₃ against annealing temperature showed smooth and continuous shrinkage at a temperature of up to 1200 °C, and the volume slightly increased above that temperature. In contrast, the volume of Y₂O₃ showed quick shrinkage at the low temperature range, and slower and smooth recovery was observed up to ～1100 °C. In the case of YAG, the recovery of volume occurred in a step-wise manner at 600–750 °C, and continuous shrinkage occurred at temperatures lower and higher than that temperature range. The activation energies for the macroscopic volume recoveries of three oxides were obtained from the Arrhenius plots of the rate coefficients. Two-stage recovery was observed for Al₂O₃, whereas more complicated recovery processes were suggested for Y₂O₃ and YAG.     

Depth profiling of Al2O3 + TiO2 nanolaminates by means of a time-of-flight energy spectrometer

Atomic layer deposition (ALD) is currently a widespread method to grow conformal thin films with a sub-nm thickness control. By using ALD for nanolaminate oxides, it is possible to fine tune the electrical, optical and mechanical properties of thin films. In this study the elemental depth profiles and surface roughnesses were determined for Al₂O₃ + TiO₂ nanolaminates with nominal single-layer thicknesses of 1, 2, 5, 10 and 20 nm and total thickness between 40 nm and 60 nm. The depth profiles were measured by means of a time-of-flight elastic recoil detection analysis (ToF-ERDA) spectrometer recently installed at the University of Jyväskylä. In TOF-E measurements ⁶³Cu, ³⁵Cl, ¹²C and ⁴He ions with energies ranging from 0.5 to 10 MeV, were used and depth profiles of the whole nanolaminate film could be analyzed down to 5 nm individual layer thickness.     

LiMgPO4:Tb,B - A new sensitive OSL phosphor for dosimetry

Optically Stimulated Luminescence (OSL) technique has emerged as a serious competitor to Thermally Stimulated Luminescence (TSL) technique in various dosimetric applications, especially after the development of crystalline alumina (Al₂O₃:C) doped with carbon. Since then, several attempts are being made to develop other possible materials for OSL based dosimetric applications. Efforts conducted in our laboratory in this direction have led to the development of a new phosphor, Lithium Magnesium Phosphate doped with terbium and boron (LiMgPO₄:Tb,B). This phosphor is prepared by solid-state diffusion method involving conventional air furnaces with operating temperature 1000 °C and easily amenable to large scale production without compromising primary dosimetric advantages. In this work we present some of the dosimetric OSL characteristics of this phosphor. The phosphor exhibits a main TSL peak at 250 °C. The phosphor also emits OSL, when the irradiated phosphor is stimulated with 470 nm light with the OSL sensitivity 1.3 times that of commercially available Al₂O₃:C. Photoluminescence (PL) emission spectrum consists of sharp lines characteristics of Tb³⁺ emission. The OSL discs made out of this phosphor are reusable up to at least 50 cycles, the phosphor exhibits dose linearity up to 1 kGy. Minimum detectable dose is found to be 20 μGy and fading of the OSL signal is found to be about 16% in four days, after which the OSL signal stabilizes.     

Development of an in situ Raman spectroscopic system for surface oxide films on metals and alloys in high temperature water

In order to directly analyze the structure of oxide films on metals and alloys in high temperature water conditions, an in situ Raman spectroscopic system has been developed, utilizing Ar-laser with sapphire/diamond window assemblies as a part of an Alloy 690 autoclave. The performance of the developed in situ Raman spectroscopic system was verified using high purity NiO, NiFe₂O₄, Cr₂O₃, and NiCr₂O₄ powders. Obtained reference Raman spectra in room temperature air environment agreed well with published results. The developed Raman system has been applied for the characterization of the surface oxide films of a nickel-base Alloy 600 in typical primary water conditions of pressurized water reactors (PWRs); water with 1000 ppm boron and 2 ppm lithium at a pressure of 18 MPa and temperatures ranging up to 350 °C. In situ Raman spectra were collected for Alloy 600 in PWR water conditions at different temperatures up to 350 °C, while the specimens were heated and then cooled. In this study, NiO, Cr₂O₃, and NiCr₂O₄ phases were observed for Alloy 600 in PWR water conditions, in reasonable agreement with earlier results of ex situ studies.     

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。     

Application of chemical interaction between (Fe,Cr) oxides and Mo oxide at high temperature for self-healing intelligence on nuclear fuel cladding in LWRs

A novel scheme for a bilayer coating with self-healing ability is proposed in this study. The candidate materials for the coatings and the potential self-healing reaction are assessed in high-temperature aqueous environments and high-temperature air. The pure Cr₂O₃ layer and the composite of Cr₂O₃ and MoO₃ are the candidate materials for the outer layer and inner layer, respectively, due to their compatibility under normal condition and fabricability. Fe₂O₃–MoO₃ reactions exhibit a potential ability to heal the cracks because of a high reaction rate under normal condition. The self-healing process proceeds via the following mechanism under normal condition: Fe₂O₃ (a corrosion product in the coolant) diffuses into the cracks on the coating and reacts with MoO₃ (inner layer) to produce the insoluble Fe₂(MoO₄)₃, which deposits and repairs the cracks. In the loss-of-coolant accident (LOCA) situation, Cr₂O₃–MoO₃ reaction is expected to strengthen the adhesion of the coating.     

The general corrosion behavior of ENiCrFe-7 weld overlay cladding material in deoxygenated high-temperature and high-pressure water

The general corrosion behavior of Alloy ENiCrFe-7 in deoxygenated high-temperature and high-pressure water was investigated. The results showed that the precipitates of Alloy ENiCrFe-7 included niobium carbide and Al-Ti-O compounds, and the weight gain increased fast firstly before 2250 h, then the weight gain slowed down. There were obvious large particles spread on denser oxide film after 3000 h exposure. Ni was present at a single chemical metallic Ni state, Feⁿ⁺ content of the outer layer was close to 60%, which was much higher than that of the matrix. The oxide film consisted of an inner layer and an outer layer, the inner layer was mainly composed of Cr₂O₃ and the outer layer was mainly composed of Fe₃O₄ and FeCr₂O₄. Finally, it is found that the preferential corrosion location of pitting was niobium carbide precipitates by in same site observation, while Al-Ti-O compounds was not dissolved in deoxygenated high-temperature and high-pressure water for 1500 h exposure. The size and number of the pitting was not significantly changed with increasing exposure time.     

Wettability of liquid caesium iodine and boron oxide on yttria-stabilized zirconia

During the Fukushima Daiichi Nuclear Power Plant accident occurred in 2011, volatile fission products (FPs) such as Cs and I had released and caused environmental contamination and public exposure, respectively. However, the release mechanism of these FPs from fuels under the accident is still not completely understood. In recent years, we have focused on the wettability of liquid FPs against solid fuels, because the interface between the fuel surface and the FPs becomes the migration pathway, which might have large influences on the release behaviour of the FPs. Here, we studied the wettability of liquid CsI and B₂O₃ on yttria-stabilized zirconia (YSZ) solid surface by the sessile drop test, where YSZ is a simulated material of the fuel. It was revealed that liquid CsI exhibited extremely high wettability against the YSZ surface with the contact angle of nearly zero. This high wettability may act to suppress the FPs release. Furthermore, it was confirmed that the crystal orientation and surface roughness of the YSZ solids have large influences on the wettability of liquid B₂O₃. The present results contribute for deep understanding of the release behaviour of the volatile FPs from fuels.     

Oxidation of Uranium Dioxide

The oxidation of UO₂ was studied by thermogravimetry and X-ray diffraction. It was clarified that the thermal history covering the first stage of the oxidation from UO₂ to U₃O UO₇ significantly influenced the rate of the oxidation of the second stage from U₃O₇ to U₃ O₈.

The entire oxidation reaction proceeded in what to all appearances, was a single stage when the specimen temperature was raised rapidly, whereas at slower rates of heating up, two distinct stages of oxidation were observed, separated by an intermediate induction period. These findings suggest the existence of a close connection between the rate of formation of the U₃O₇ phase and the rate of the subsequent oxidation of this phase: A slow formation of U₃O₇ would tend to prolong the induction period preceding the second stage of the oxidation. A similar effect was observed also with annealing of the intermediate U₃O₇ at 200°C: The increase of annealing time prolonged the induction stage.

The rate of the second stage oxidation was fairly well expressed by Johnson & Mehl's equation, log (1/(1-y/)=(1/2.303)kⁿtⁿ . The time exponent n in this equation varied in the range of 1.0~2.5, and the rate constant k of 1.15×10^?4~2.04 ×10^?1 min^?1, depending on the experimental conditions.     

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.     

Boiling and drying accident of high-level liquid waste in a reprocessing plant: Examination of the NO2 and NO generation using the simulated waste

ABSTRACT

NO₂ and NO generated during a boiling and drying accident, which affects the release of volatilized radioactive Ru into the atmosphere, were examined using various samples including simulated high-level liquid waste and a thermogravimetric analyzer. NO₂ and NO in the gas flowing out of the analyzer were measured separately using a NOx analyzer equipped with NO₂ and NO sensors. The samples were heated to 600°C at constant heating rates of mainly 0.2 and 1°C min^?1 that was adopted taking into account the decay heat of high-level liquid waste. It was found that under 180°C some nitrates in the liquid waste mainly separated their nitrate groups as HNO₃ without generating NOx (a mixture of NO and NO₂) and above 300°C the residual HNO₃ in the waste participated in thermal decomposition generating NOx. The generation rates of NO₂ and NO were obtained as a function of time using Arrhenius type equations, and the O₂ rate was derived from these equations using the stoichiometry of the reactions that generate NO₂, NO, and O₂.     

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.     

Effects of Mg-ion implantation in α-Al2O3 and α-Al2O3:Mg crystals: Electrical conductivity and electronic structure changes

Undoped and Mg-doped α-Al₂O₃ single crystals were implanted with Mg ions, with an energy of 90 keV and a fluence of 10¹⁷ ions/cm². DC electrical measurements using the four-point probe method, between 295 and 428 K, were used to characterize the electrical conductivity of the implanted area. Measurements in this temperature range indicate that the electrical conductivity after implantation is thermally activated with an activation energy of about 0.03 eV both in undoped and in reduced Mg-doped α-Al₂O₃ crystals, whereas the activation energy in oxidized Mg-doped α-Al₂O₃ crystals remains close to that before implantation. The I-V characteristics of the latter samples reveal a blocking behavior of the electrical contacts on the implanted area in contrast to the ohmic contacts observed in α-Al₂O₃ single crystals with the c-axis perpendicular to the broad face, where the Mg ions were implanted. We conclude that the enhancement in conductivity observed in the implanted regions is related to the intrinsic defects created by the implantation, rather than to the implanted Mg ions. The relationship between the oxygen vacancy concentrations at different stages of etching and the changes in the electronic structure, the chemical bonding, and the Al³⁺(2p)/O²⁻(1s) and Mg²⁺(1s)/O²⁻(1s) relative intensities was studied by X-ray Photoemission Spectroscopy.