Gd2O3-Nd2O3-ZrO2-CeO2体系的高温固相反应研究

为研究Gd₂O₃-Nd₂O₃-ZrO₂-CeO₂四元氧化物体系的高温固相反应,以Gd₂O₃、Nd₂O₃、ZrO₂、CeO₂混合粉体为原材料,在1 673 K和1 773 K温度下煅烧24、48、72 h,分别制备了系列样品,并对合成样品进行了XRD和SEM分析。结果表明,合成产物为具有缺陷萤石相且伴有少量烧绿石相的Gd_2-xNd_xZr_2-xCe_xO₇（0≤x≤2）晶体化合物。随着煅烧温度的升高和煅烧时间的延长,产物中立方烧绿石相的化合物增多,晶粒尺寸变大,且有少量未知相生成。进而探讨了锆基陶瓷固化多核素的潜在应用,并提出了未来研究的相关热点问题。     

FCM燃料压水堆弥散可燃毒物中子学分析

为将全陶瓷微胶囊封装（FCM）燃料应用于小型压水堆,对FCM燃料组件开展了可燃毒物中子学设计与分析。通过寿期初引入负反应性、寿期内消耗速率和寿期末残留3个方面,对弥散在SiC基体中的弥散型可燃毒物Gd₂O₃、Er₂O₃、Sm₂O₃、Eu₂O₃、Dy₂O₃及HfO₂进行评价。FCM燃料中TRISO颗粒核芯直径达800 μm,燃料颗粒自屏效应强烈,在RMC程序中引入随机介质计算功能,对FCM燃料进行随机几何建模,保证了反应性计算精度。分析表明：Er₂O₃可作为FCM燃料堆芯的候选可燃毒物,Gd₂O₃和Eu₂O₃需结合堆芯开展进一步研究,Sm₂O₃、Dy₂O₃及HfO₂的反应性惩罚过大,不适合作为FCM燃料可燃毒物。     

氯化锂熔盐中八氧化三铀电解还原基础研究

将氧化物乏燃料直接电解还原为粗金属的过程是目前以电解还原-电解精炼为特征的主流干法后处理流程的重要步骤。二氧化铀（UO₂）是乏燃料的最主要成分,将致密的UO₂芯块转化为八氧化三铀（U₃O₈）粉末后,再进行电化学还原能有效提高还原速率。因此,以U₃O₈为研究对象,开展其在氯化锂（LiCl）熔盐中的电解还原机理研究,对后处理干法流程的开发具有重要的现实意义。本文在650 ℃的LiCl熔盐中,采用循环伏安法和恒电位电解法,研究U₃O₈的电解还原行为;对电解后的样品,运用XRD、SEM等手段分析其组成和形貌,并推测相应的还原机理。     

影响CaCl2-NaCl熔盐电脱氧法制备金属Zr的工艺条件

将氧化物转化为金属是熔盐电解精炼干法后处理氧化物乏燃料流程的关键步骤之一。在等摩尔CaCl₂-NaCl混合熔盐体系中,以石墨棒为阳极,采用高温烧结后的ZrO₂模拟UO₂开展了电脱氧制备金属Zr的FFC剑桥工艺条件优化。研究了工艺条件（槽电压、电解时间、烧结温度和电解温度等）对电脱氧制备Zr的影响。采用场发射扫描电子显微镜(SEM)和X射线衍射(XRD)分别分析了电解前后ZrO₂阴极的微观结构和物相组成。优化后的工艺条件为：电压3.4 V、电解时间12 h、烧结温度900 ℃和电解温度722 ℃。同时,研究结果表明, ZrO₂电脱氧还原为Zr时,存在中间产物CaZrO₃和ZrO。     

H2C2O4对TODGA萃取Nd3+的影响

以N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)为代表的酰胺荚醚类萃取剂可以有效萃取高放废液中的An(Ⅲ)和Ln(Ⅲ),为防止Zr⁴⁺、Pd²⁺等裂片元素萃入有机相,通常需要加入H₂C₂O₄作为水相络合剂,目前,H₂C₂O₄对TODGA萃取Ln(Ⅲ)的影响尚未报道。本工作研究了HNO₃、H₂C₂O₄浓度对TODGA或TODGA+TBP体系萃取Nd³⁺的影响,同时测定了有机相中的H₂C₂O₄浓度,并用紫外-可见吸收光谱分析了有机相中的H₂C₂O₄与有机相中Nd³⁺的配位情况。研究结果表明：HNO₃浓度在1.0~3.0 mol/L的范围内,Nd³⁺的分配比D(Nd³⁺)随HNO₃浓度的增加而增加;H₂C₂O₄浓度在0.1~0.5 mol/L的范围内,D(Nd³⁺)随H₂C₂O₄浓度的增加而增加。HNO₃浓度在1.0~3.0 mol/L的范围内,萃入有机相中H₂C₂O₄浓度随HNO₃浓度的增加而减小,且存在于有机相中的H₂C₂O₄并未与有机相Nd³⁺配位。     

高温结晶合成Mn2O3@MoS2复合材料及其对铀的吸附性能

采用高温熔盐电解法合成了MoS₂,为了提高MoS₂对铀的吸附性能,以MoS₂为基底复合Mn₂O₃。MoS₂的片层结构有效地分散了Mn₂O₃的团聚,同时引进了亲铀氧基团。采用电子扫描显微镜及能谱(SEM & EDS)、X射线衍射仪(XRD)、Zeta电位仪等对Mn₂O₃@MoS₂复合材料进行了表征,表征结果表明,高温结晶合成的Mn₂O₃@MoS₂复合材料具有完整的微观形貌和稳定的晶体结构。通过静态吸附批实验探究了在不同变量下Mn₂O₃、MoS₂和Mn₂O₃@MoS₂三个材料对溶液中铀的吸附效果,结果表明,Mn₂O₃@MoS₂的吸附性能优于Mn₂O₃和MoS₂,在pH=5.5时,吸附平衡时间为90 min,吸附动力学遵循准二级动力学模型,吸附等温线符合Langmuir模型。Mn₂O₃@MoS₂的单层饱和吸附容量为117.5 mg/g,在293.15~318.15 K的温度梯度中,升温有利于吸附进行。     

基于卷积神经网络模型的Gd2O3/6061Al中子屏蔽材料的力学性能预测

提出了一种卷积神经网络模型来预测Gd₂O₃/6061Al中子屏蔽材料的力学性能。以Gd₂O₃/6061Al中子屏蔽材料的EBSD微观形貌及其相应的拉伸性能作为数据集来训练及验证卷积神经网络模型。结果表明：使用多个显微图像,不需任何人工图像处理,卷积神经网络可得到良好的训练结果,其性能优于传统的测试方法;卷积神经网络捕捉到晶粒的存在和晶粒的一些统计信息;晶粒数目和晶粒大小之间具有很强的相关性。     

α/γ相比率调控对超音速等离子喷涂Al2O3阻氚涂层微结构及性能的影响

采用超音速等离子喷涂技术在中国低活化马氏体钢表面制备不同α/γ相比率的Al₂O₃阻氚涂层,研究了α/γ相比率调控对Al₂O₃涂层微观结构、力学性能和耐电化学腐蚀性能的影响。利用掠入射X射线衍射（GIXRD）和扫描电子显微镜（SEM）表征Al₂O₃涂层的微观结构、粘结拉伸试验法和纳米压痕仪表征涂层的力学性能、动电位极化曲线法测试涂层的耐电化学腐蚀性能。研究结果显示：通过调控特征喷涂参数（CPSP）,Al₂O₃涂层中α相含量从78.6%至24.4%可控调节,且孔隙率从2.8%降低至1.5%;α相含量为78.6%的Al₂O₃涂层硬度为(11.500±0.575) GPa,约为高γ相含量(75.6%)涂层的2倍;且高α相含量(78.6%)涂层的腐蚀电流密度较高γ相含量(75.6%)涂层的腐蚀电流密度低1个数量级。以上结果表明,高α相含量(78.6%)的Al₂O₃涂层具有更优异的力学性能、耐电化学腐蚀性能以及耐Cl^-扩散穿透能力,具有应用于聚变堆结构材料表面阻氚涂层的潜能。     

NaCl-KCl熔盐体系电解制备金属铈工艺研究

为优化熔盐电解还原制备金属铈的工艺条件,开展了NaCl-KCl熔盐体系中CeCl₃的电化学行为及电解工艺研究。结果表明,在830 ℃下,以钼棒为工作电极、石墨棒为对电极、阴极电位高于1.9 V(Ag/AgCl为参比电极,下同)时,Ce³⁺可快速电解,提高Ce3+浓度有利于反应的进行。槽电压为4.41 V、相应的阴极电位为2.27 V时,电流效率最佳。固定阳极面积改变阴极面积的研究结果显示,随着阴极面积的减小,槽电压逐渐升高。实验条件下,槽电压随电极中心距的变化是线性的,与电极中心距的改变相比,电流的变化对槽电压的影响更显著。     

掺杂Cr2O3对UO2芯块烧结行为的影响

提高燃料燃耗的一个有效手段是通过增大UO₂晶粒尺寸来减少元件内部气体压力,在大晶粒UO₂芯块中,裂变气体到达晶界表面的距离增加,因而裂变气体的释放速率降低,元件内部气体压力的增高缓慢。本文研究了添加Cr₂O₃对UO₂晶粒尺寸的影响。对纯UO₂、添加0.5% Cr₂O₃及5% Cr₂O₃ 3种配方的芯块进行了试验,在5%H₂Ar保护下,以10 ℃/min和5 ℃/min的升温速率升温至1 700 ℃,然后烧结2 h或4 h,对比纯UO₂芯块与添加Cr₂O₃的芯块发现,添加Cr₂O₃可有效增大晶粒尺寸;较长的烧结时间可促进晶粒长大;较低的升温速率也使晶粒长大。烧结过程产生液相烧结,液相浸润晶粒边界,促进晶粒长大。     

Heavy ion irradiation effects in the rare-earth sesquioxide Dy2O3

Polycrystalline pellets of the rare-earth sesquioxide Dy₂O₃ with cubic C-type rare-earth structure were irradiated with 300 keV Kr²⁺ ions at fluences up to 5 × 10²⁰ Kr/m² at cryogenic temperature. Irradiation-induced microstructural evolution is characterized using grazing incidence X-ray diffraction (GIXRD) and transmission electron microscopy (TEM). In previous work, we found a phase transformation from a cubic, C-type to a monoclinic, B-type (C2/m) rare-earth structure in Dy₂O₃ during Kr²⁺ ion irradiation at a fluence of less than 1 × 10²⁰ Kr/m². In this study, we find that the crystal structure of the top and middle regions of the implanted layer transform to a hexagonal, H-type (P6₃/mmc) rare-earth structure when the irradiation fluence is increased to 5 × 10²⁰ Kr/m²; the bottom of the implanted layer, on the other hand, remains in a monoclinic phase. The irradiation dose dependence of the C-to-B-to-H phase transformation observed in Dy₂O₃ appears to be closely related to the temperature and pressure dependence of the phases observed in the phase diagram. These transformations are also accompanied by a decrease in molecular volume (or density increase) of approximately 9% and 8%, respectively, which is an unusual radiation damage behavior.     

Cleaning of materials contaminated with metal oxides through supercritical fluid extraction with CO2 containing TBP

Studied was an application of supercritical fluid extraction (SFE) to cleaning of the materials contaminated with metal oxides. By using supercritical CO₂ including chemical complexes of tri-n-buthylphosphate (TBP) and HNO₃, lanthanide was recovered from oxide mixtures placed in a pressure vessel. The lanthanide oxide was dissolved with TBP-HNO₃ and extracted with TBP in supercritical CO₂. This cleaning method reduces volume amount of liquid waste arising from treatment of the contaminated materials. Being applied to a mixture of Gd₂O₃ and SrO, we found that Gd was selectively recovered and Sr was not found in the recovered solution. Gd was also selectively recoverd when a mixture of Gd₂O₃ and ZrO₂ was treated. This selective nature of decontamination is an additional advantage of the SFE with TBP-HNO₃ complex. This method would be applicable to the selective cleaning of materials contamined with radioactive oxides such as UO₂/PuO₂.     

Separation of plutonium from lanthanum by electrolysis in LiCl–KCl onto molten bismuth electrode

This work presents a study on the electroseparation of plutonium from lanthanum using molten bismuth electrodes in LiCl–KCl eutectic at 733 K. The reduction potentials of Pu³⁺ and La³⁺ ions were measured on a Bi thin film electrode using cyclic voltammetry (CV). A difference between the peak potentials for the formation of PuBi₂ and LaBi₂ of approximately 100 mV was found. Separation tests were then carried out using different current densities and salt phase compositions between a plutonium rod anode and an unstirred molten Bi cathode in order to evaluate the efficiency of an electrolytic separation process. At a current density of 12 mA/cm²/wt% (Pu³⁺), only Pu³⁺ ions are reduced into the molten Bi electrode, leaving La³⁺ ions in the salt melt. Similar results were found at two different Pu/La concentration ratios ([Pu]/[La] = 4 and 10). At a current density of 26 mA/cm²/wt% (Pu³⁺), co-reduction of Pu and La was observed as expected by the large negative potential of the Bi cathode during the separation test.     

Design of a gadolinia bearing mixed-oxide fuel assembly for pressurized water reactors

A study on neutronics design of a gadolinia (Gd₂O₃) bearing mixed-oxide (MOX) fuel assembly (MOX-UO₂ (Gd₂O₃) assembly) was performed for the purpose of suppressing the use of fresh lumped burnable poison rods (BPRs). The MOX-UO₂ (Gd₂O₃) assembly investigated consists of MOX and UO₂ (Gd₂O₃) fuel rods, which have already been verified through both fabrication and irradiation experiences. In all, 16 UO₂ (10 wt% Gd₂O₃) fuel rods are located at every corner and the peripheral region of the MOX-UO₂ (Gd₂O₃) assembly in order to reduce the power peaking of MOX fuel rods due to the thermal neutron inflow, and to reduce the reactivity penalty at the end of cycle (EOC). Since fresh BPRs are not expected to be inserted and UO₂ (Gd₂O₃) fuel rods are located at every corner of the assembly, the number of splits in plutonium (Pu) content can be only two, which is less than three splits required for a standard MOX assembly. Core characteristics of an equilibrium core loaded with MOX-UO₂ (Gd₂O₃) assemblies are evaluated and it is verified that adoption of the MOX-UO₂ (Gd₂O₃) assembly is effective to avoid the use of fresh BPRs with securing both the core safety and cycle length. The simplication of the splits in Pu content is also supposed to be beneficial, since it has the possibility of reduce MOX fuel fabrication costs.     

液体阴极法回收盐渣中钚离子的模拟实验

采用液体阴极法电解NaCl-KCl-CeCl_3熔盐,回收熔盐中的铈离子以模拟高温化学工艺废盐渣中钚离子的回收。研究了初始CeCl_3浓度、温度、阴极电流密度对电解指标的影响,确定了初始CeCl_3质量分数为5%、温度750℃、阴极电流密度0.10A/cm~2时,熔盐对Ce的净化系数可达130,盐渣中残留的CeCl_3质量分数可降低到0.04%以下。实验证实了液体阴极法有望应用于废盐渣中钚离子的回收。