(U,Gd)O2芯块试验与工业生产

文章介绍在宜宾核燃料元件厂(YFP)生产线上进行(U,Gd)O2芯块工业规模的生产试验及产品合格性鉴定,对试验结果进行讨论和评价.结果表明:YFP的(U,Gd)O2芯块生产线完全具备工业生产能力,并实现(U,Gd)O2芯块制造的国产化.     

(U,Gd)O_2可燃毒物燃料芯块制造工艺及其主要性能

介绍了中国核动力研究设计院(U,Gd)O2可燃毒物燃料芯块制造生产线所使用的原材料UO2粉末、Gd2O3粉末、(U,Gd)3O8粉末以及添加剂硬脂酸锌和草酸铵的主要性能,同时描述了混料、制粒、成型、烧结和磨削等制造工艺过程及其产品(U,Gd)O2芯块的主要性能,并对制造过程中有关工艺控制参数进行了讨论。     

Gd2O3-UO2芯块中添加U3O8研究

Gd2O3-UO2可燃毒物燃料是近年来核电站采用较为普遍的可燃毒物之一。传统观点认为在芯块制造过程中添加U3O8粉末会降低芯块的烧结密度．本文研究了在Gd2O3-UO2芯块基体密度-94％T．D的基础上．添加不同品比例由AUC煅烧得到的U3O8粉末，经成型，H2/H2O气氛中1750℃烧结后表明．随着U3O8加入量的增加，芯块的密度也随之增加，U3O8添加量大于40wt％时芯块的密度达到-97％T.D．,U3O8的加入相当于起到了助烧剂的作用．这一现象和传统的U3O8降低芯块密度的观点正好相反．而芯块的平均晶粒尺寸-8μm。     

烧结温度与Th含量对(Th,U)O_2芯块密度影响

研究烧结温度和Th含量对(Th,U)O2芯块密度的影响,计算不同Th含量的(Th,U)O2芯块烧结活化能,通过扫描电镜(SEM)分析(Th,U)O2芯块中气孔的变化迁移过程。结果表明:在相同烧结温度下,(Th,U)O2芯块密度随Th含量的增大而降低;随烧结温度升高,芯块密度增大,在此过程中存在一个使芯块快速致密化的烧结势垒温度;(Th,U)O2芯块烧结活化能随Th含量的增大而增大,Th含量(摩尔分数)为20%、50%、80%的(Th,U)O2芯块的烧结活化能分别为277.65、300.70、380.99 k J/mol;在Th含量为20%的(Th,U)O2芯块中,气孔呈球形分布于晶界交汇处。     

Gd2O3-UO2芯块晶粒尺寸的影响因素研究

用光学显微镜和图象分析仪研究了影响Gd2O3-UO2芯块晶粒尺寸的因素。对烧结气氛、混料方式、芯块在烧结炉中的位置、以及在UO2芯块中添加U3O8、草酸铵和助烧剂（Al、Ti、V的氧化物）等给Gd2O3-UO2芯块晶粒尺寸带来的影响进行了研究。结果表明,球磨工艺、添加助烧剂和微氧化气氛烧结等都有利于芯块的晶粒生长,晶粒大小分布均匀;添加U3O8和草酸铵对芯块的晶粒生长无明显的影响。     

UO2?-Er2O3燃料芯块制备技术初步研究

对Er₂O₃质量分数为4.32%的UO₂-Er₂O₃可燃毒物燃料芯块的制备技术进行了初步研究。通过对比不同工艺条件（混料、成型、烧结）下,芯块的外观完整度、密度、晶粒度等性能,初步得到了UO₂-Er₂O₃燃料芯块的制备技术。试验表明:干法球磨混合6?h,添加5‰的聚乙烯醇（PVA）,300~350?MPa压力下冷压成型,1700~1750℃、H₂气氛中烧结2~3?h,可得到外观完整、密度大于等于95%理论密度（T.D.）、晶粒尺寸大于8?μm的UO₂?-Er₂O₃燃料芯块。      

添加Al2O3和SiO2的大晶粒UO2芯块制备研究

研究了Al2O3和SiO2添加剂对UO2芯块晶粒尺寸的影响.结果表明加入少量的Al2O3和SiO2,可有效促进烧结过程中UO2芯块的晶粒度长大,过量加入则会阻碍烧结过程中UO2芯块的致密化;在添加量一定的情况下,添加不同比例的Al2O3和SiO2,对芯块晶粒尺寸有较大影响,只添加SiO2,对芯块晶粒尺寸影响不大,Al2O3添加量增加,芯块晶粒尺寸随之增加;添加Al2O3和SiO2促进UO2芯块晶粒长大的机制是在烧结期间发生了液相烧结.     

H2O2活化蒙脱石对溶液中U(Ⅵ)的吸附

利用H₂O₂对蒙脱石进行活化，获得了活化蒙脱石吸附材料(A_X-MMT)，采用X射线衍射(XRD)、傅里叶红外谱图(FTIR)、透射电镜(TEM)、扫描电镜(SEM)、比表面分析(BET)、表面Zeta电位分析等手段对活化样品进行了表征；采用静态批量实验法，考察了H₂O₂浓度、pH值、接触时间和共存阴阳离子对U(Ⅵ)在A_X-MMT上吸附率的影响。结果表明：活化保留了蒙脱石基础结构，其阳离子交换容量(CEC)有所减少，但层间距、比表面积、孔隙体积、表面酸位点和表面Zeta电位均有明显提升，对溶液中U(Ⅵ)的吸附性能显著增强；在最佳活性和吸附条件下(H₂O₂质量分数、pH值和接触时间分别为10%、6和24 h)，蒙脱石对U(Ⅵ)的吸附性能提升了8.5倍，吸附行为符合准二级吸附动力学模型；在共存阴阳离子的干扰下，H₂O₂活化蒙脱石能对U(Ⅵ)展现良好的吸附性能。     

光催化材料CdS/TiO2的制备及其光催化还原U(Ⅵ)性能研究

为探讨光催化还原技术在含铀废水中对U(Ⅵ)的还原性能,本文采用分步沉淀法制备了CdS/TiO₂复合纳米粒子,利用SEM、XRD、DRS等手段对其进行表征,并通过光催化还原U(Ⅵ)试验考察了材料的光催化还原活性。结果表明,CdS/TiO₂复合纳米粒子是由锐钛矿型、金红石型二氧化钛和立方晶型硫化镉组成的光催化材料,其颗粒大小为30～50 nm;与TiO₂相比,CdS/TiO₂复合纳米粒子的吸收光谱发生了明显的红移。CdS/TiO₂复合纳米粒子表现出较好的光催化还原U(Ⅵ)活性,在模拟废水pH=6.0、材料用量1.0 g/L时,对U(Ⅵ)的光催化还原效率最高,达99.13%;在真实废水中对U(Ⅵ)的还原率为90.4%,经处理的含铀废水达到国家规定的排放标准。     

HNO3介质中U(Ⅳ)还原Np(Ⅴ)的动力学

采用分光光度法研究了HNO₃溶液中U(Ⅳ)还原Np(Ⅴ)的反应,获得了动力学方程-dc (Np(Ⅴ))/dt=kc(Np(Ⅴ))c^0.7 (U(Ⅳ))c^1.9 (H⁺)c (NO^-₃),25℃时反应速率常数k=(6.37±0.49)×10^-3 L^3.6/(mol 3.6•min),反应活化能E_a=60.13 kJ/mol。结果表明,浓度为0~4.2×10^-2mol/L的U(Ⅵ) 对U(Ⅳ)还原Np(Ⅴ)的反应几乎没有影响,并探讨了可能的反应机理。     

Thermal conductivities of irradiated UO2 and (U, Gd)O2 pellets

Thermal diffusivities of UO₂ and (U, Gd)O₂ pellets irradiated in a commercial reactor (maximum burnups: 60 GWd/t for UO₂ and 50 GWd/t for (U, Gd)O₂) were measured up to about 2000 K by using a laser flash method. The thermal diffusivities of irradiated UO₂ and (U, Gd)O₂ pellets showed hysteresis phenomena: the thermal diffusivities of irradiated pellets began to recover above 750 K and almost completely recovered after annealing above 1400 K. The thermal diffusivities after recovery were close to those of simulated soluble fission products (FPs)-doped UO₂ and (U, Gd)O₂ pellets, which corresponded with the recovery behaviors of irradiation defects for UO₂ and (U, Gd)O₂ pellets. The thermal conductivities for irradiated UO₂ and (U, Gd)O₂ pellets were evaluated from measured thermal diffusivities, specific heat capacities of unirradiated UO₂ pellets and measured sample densities. The difference in relative thermal conductivities between irradiated UO₂ and (U, Gd)O₂ pellets tended to become insignificant with increasing burnups of samples.     

Homogeneity characterisation of sintered (U,Gd)O2 pellets by X-ray diffraction

(U,Gd)O₂ sintered pellets are fabricated by different methods. The homogeneity characterisation of the Gd content seems to be necessary for a production control to qualify the process and the final product obtained. In this paper, we propose an analysis of the X-ray diffraction powder patterns through the Rietveld method, in which the differences between the experimental and the calculated data proposed from a crystalline structure model are evaluated. This result allows us to determine the cell parameters, that can be correlated with the Gd concentration, and the existence of other phases with different Gd contents.     

Thermophysical properties of (U,Y)O2

We prepared polycrystalline pellets of (U,Y)O₂, containing YO_1.5 up to 11 mol.%. We performed indentation tests on the pellets, and evaluated the Young’s modulus and hardness. We measured the heat capacity and the thermal diffusivity, and evaluated the thermal conductivity. We succeeded in evaluating the effect of Y content on the thermophysical properties of (U,Y)O₂. We revealed that the Young’s modulus, hardness, and thermal conductivity of (U,Y)O₂ decreased with increasing the Y content.     

Properties of lenticular pores in UO2, (U,Pu) O2 and PuO2

Lenticular pore migration rates in oxide muclear fuels were experimentally measured in out-of-pile heating experiments. It is deduced that those pores which are in part responsible for the formation of columnar grains, are only produced in the absence of relevant amounts of filling gas. Specimens containing important concentrations of He, produced by Pu alpha decay, show columnar grain restructuring by grain boundary migration. Some consequences are drawn concerning the possible role played by lenticular pores in the mechanisms of fission gas release from nuclear fuels.     

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.     

Calorimetric measurements on (U,Th)O2 solid solutions

Enthalpy increments of urania - thoria solid solutions, (U_0.10Th_0.90)O₂, (U_0.50Th_0.50)O₂ and (U_0.90Th_0.10)O₂ were measured by drop calorimetry in the temperature range 479 - 1805 K. Heat capacity, entropy and Gibbs energy function were computed. The heat capacity measurements were carried out also with differential scanning calorimetry in the temperature range 298 - 800 K. The heat capacity values of (U_0.10Th_0.90)O₂, (U_0.50Th_0.50)O₂ and (U_0.90Th_0.10)O₂ at 298 K are 59.62, 61.02, 63.56 J K⁻¹ mol⁻¹, respectively. The results were compared with the data available in the literature. From the study, the heat capacity of (U,Th)O₂ solid solutions was shown to obey the Neumann - Kopp’s rule.     

Separation of uranium from (U, Th)O2 and (U, Pu)O2 by solid state reactions route

Solid state reactions of UO₂, ThO₂, PuO₂ and their mixed oxides (U, Th)O₂ and (U, Pu)O₂ were carried out with sodium nitrate upto 900 °C, to study the formation of various phases at different temperatures, which are amenable for easy dissolution and separation of the actinide elements in dilute acid. Products formed by reacting unsintered as well as sintered UO₂ with NaNO₃ above 500 °C were readily soluble in 2 M HNO₃, whereas ThO₂ and PuO₂ did not react with NaNO₃ to form any soluble products. Thus reactions of mixed oxides (U, Th)O₂ and (U, Pu)O₂ with NaNO₃ were carried out to study the quantitative separation of U from (U, Th)O₂ and (U, Pu)O₂. X-ray diffraction, X-ray fluorescence, thermal analysis and chemical analysis techniques were used for the characterization of the products formed during the reactions.     

Production of CO during burnup of (Th,U)O2 kerneled HTR fuel particles

The CO content of irradiated (Th, U)O₂ kerneled HTR fuel particles has been measured by mass spectrometry. An evaluation of all the data thus obtained showed that the oxygen release, O/f (atoms per fission), during irradiation is governed by thermodynamic equilibrium; O/f is a function of the irradiation temperature $\text{T}$(K), the initial Th/U-235 ratio $\text{N}$, and the burnup $\text{F}$ (fissions per initial heavy metal atom). Within the limits of $\text{1073 < T < 2273}$, $\text{4 < N <50}$, and $\text{0.04 < F < 0.17}$, the oxygen release can be represented by the expression $\text{log}{}_{10}\text{O/f = 0.96 ? 4420/T + 0.4 log}{}_{10}\text{N + 0.3 log}{}_{10}\text{F}$.The attainment of equilibrium proceeds rather slowly; at 1473 K it takes about 130 h to reach 99% of the equilibrium value.Coated particles which had undergone large fission-product losses showed significantly increased oxygen release values.