稀土氧化物Gd2O3、Nd2O3、Sm2O3和Dy2O3在KCl-LiCl-Li2O熔盐中的电解

采用循环伏安法和计时电位法研究了Li₂O在KCl-LiCl熔盐中的电化学行为,并利用卷积伏安法计算了923 K下O₂^-在KCl-LiCl熔盐中的扩散系数（D),得到D=0.5×10^-5 cm²/s。以Gd₂O₃、Nd₂O₃、Sm₂O₃和Dy₂O₃为阴极,在KCl-LiCl-Li₂O(w=1%)熔盐中进行电解（恒电压3.40 V、电解温度923 K、电解时间25 h）。通过X射线衍射分析(XRD),证实稀土氧化物被部分还原为金属,并分析了电解过程中可能发生的反应。同时利用PRS模型（该模型可将固态阴极内离子的极限扩散速率与固态氧化物孔隙P、金属/氧化物摩尔体积R、阴极还原后的体积收缩率S等参数关联）分析了这些稀土氧化物的电解还原模型,得到Gd₂O₃、Nd₂O₃、Sm₂O₃和Dy₂O₃的最优孔隙率分别为18.7%、24.2%、30.6%、16.7%,最短电解时间分别为133、157、143、119 h,将这些结果与电解实验结果进行对比,发现阴极的孔隙率和电解时间均不满足金属氧化物完全被还原的要求,并给出了相应的解释。     

Investigations of the melting behaviour of the U–Zr–Fe–O system

During a severe nuclear accident, the UO₂ fuel rods, Zircaloy cladding, guide tubes, absorber and steel structural components inside the reactor pressure vessel overheat and a series of interactions between these elements and the steam atmosphere occur. These produce more heat in addition to the decay heat and result in a liquid corium of oxidic and metallic phases depending on the exact conditions and processes. A major systems resulting from this is the U–Zr–Fe–O system. High-temperature data for this system is important in order to be able to model these interactions. The Joint Research Centre, Institute for Transuranium Elements (JRC-ITU) has been examining the melting ranges for this system over the whole FeO range by means of a specialized laser flash technique that achieves very high temperatures and avoids crucible contamination. The melted zones were examined for their structure, composition and for estimation of the liquidus and solidus temperatures. The results showed that with FeO contents of over 20mol% there was a very large melting range that would permit long liquid cooling times and extend the relocation of fuel material within the reactor pressure vessel. Based on these results, the main phase regimes expected under severe accident conditions could be identified.     

液态H_2O、HDO、D_2O、HTO、DTO、T_2O的红外吸收光谱

本文主要介绍在4000—400cm~(-1)范围内用天然水、99.886 mol.%重水配制的不同浓度的H_2O-HDO—D_2O混合物体系,含氘10.0%(原子分数)的H_2O—HTO-T_2O混合物体系及含氘41.2%(原子分数)的D_2O-DTO-T_2O混合物体系;研究了液态H_2O、HDO、D_2O、HTO、DTO和T_2O的红外吸收光谱,并用经验规律计算了氘水的红外吸收峰的波数值。由实验得到的光谱吸收峰位置与文献值和计算值相一致。     

聚砜中空纤维膜去除气流中的CO2、H2O和O2

在环境温度24℃,用空压机提供气源,通过改变压力和流速等操作条件,用自建实验装置进行了聚砜膜去除空气气流中CO2、H2O和O2的实验研究.监测分析原料气、产品气和渗透气中各组分的浓度,计算各种气体的脱除率、传质系数和渗透系数等,评估了聚砜膜对这些组分的分离性能.实验结果表明,当压力超过320 kPa时,对应原料气流速大...     

Dynamics of deuterium retention and sputtering of Li–C–O surfaces

Chemistry as well as sputtering and reflection dynamics of lithiated carbon material, bombarded by slow hydrogen atoms are studied. We present a realistic method for computational simulation of the dynamics of the polar Li–C–O–H material dynamics. It is based on an approximate, semi-empirical quantum mechanics of electrons and classical mechanics of nuclei. Results are validated qualitatively by comparison with experiments and with a first principle DFT computations. In particular, we explain observed details of the hydrogen bonding chemistry in lithiated carbon, showing that incoming hydrogen interacts preferably with Li-C rather than C structures.     

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。     

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。     

Tensile and Charpy impact properties of an ODS ferritic/martensitic steel 9Cr–1.8W–0.5Ti–0.35Y2O3

A 9Cr-ODS ferritic/martensitic steel with a composition of 9Cr–1.8W–0.5Ti–0.35Y₂O₃ was fabricated by mechanical alloying and hot isostatic pressing, followed by hot rolling. Tensile properties were measured at room temperature (23 °C) and 700 °C in the rolling direction (LT) and the transverse direction (TL). The ultimate tensile strength (UTS) of the as-rolled samples in both directions reached 990 MPa at 23 °C, and still maintained at 260 MPa at 700 °C. The tensile strength and elongation of the rolling direction was greater than that of the transverse direction. The Charpy impact was tested from −100 to 100 °C in the LT direction. The lower shelf energy (LSE) was more than 65% of the upper shelf energy (USE). The total absorbed energy was separated into the energies for crack initiation and propagation. The propagation energy was always higher than the initiation energy in the range of temperatures tested. The ductile-to-brittle transition temperature (DBTT) of the rolled 9Cr ODS evaluated by an absorbed energy curve was about 0 °C. However, the high LSE and the fracture surface that still contained dimples at lower shelf indicated good toughness of the as-rolled 9Cr ODS steels at temperature of −60 °C.     

A mechanism for the sintered density decrease of UO2–Gd2O3 pellets under an oxidizing atmosphere

A mixture of UO₂ and Gd₂O₃ powders was pressed into compacts and sintered under various atmospheres ranging from reducing to oxidizing gases. The sintered density of UO₂–10 wt% Gd₂O₃ pellets decreases with increasing oxygen potential of the sintering atmosphere. Dilatometry and X-ray diffraction studies indicate that the delay of densification takes place between 1300°C and 1500°C, along with the formation of (U,Gd) O₂. A very large solubility of Gd₂O₃ in UO₂ relative to the reverse solubility might cause Gd ions to diffuse into UO₂ so directionally that new pores are produced at the places of Gd₂O₃ particles. The new pores may be difficult to shrink and thus lead to the density decrease under an oxidizing atmosphere but not under a reducing atmosphere, because a driving force for the shrinkage of new pores may be smaller under an oxidizing atmosphere than under a reducing atmosphere.     

电解法制备高纯度18O2

采用自行设计制造的石英玻璃电解装置,以重氧重水为原料,通过碱性介质电解法进行了18O气体的制备,在原料重氧重水18O的摩尔分数>80%条件下,最终制得18O气体中18O2摩尔分数达63.66%,表明整个电解系统气密性良好。此外,制得的气体能够满足电子回旋共振离子源提供18O重离子束的实验要求。     

Oxygen potential measurement of (Pu0.928Am0.072)O2–x at high temperatures

The oxygen potentials of (Pu_0.928Am_0.072)O_2–x were measured as a function of oxygen to metal ratio (O/M) in the temperature range from 1473 to 1873 K by the gas equilibrium method using thermogravimetry. The measured data were about 200 kJ/mol higher in the O/M ratio range from 2.00 to 1.96 and about 50 kJ/mol higher in the reducing region (below O/M ratio = 1.94) compared with those of PuO_2–x. The measured oxygen potentials were analyzed by the point defect chemistry method. From this analysis, the oxygen potential of (Pu_0.928Am_0.072)O_2–x was represented as a function of O/M ratio and temperature and calculated results were consistent with the measured data.     

Development of thermodynamic databases in the system U–Zr–Ce–Cs–Fe–B–C–I–O–H for application to simulating phase equilibria in severe nuclear accidents

In case of severe nuclear accidents involving melt down of nuclear fuels at high temperatures, it is of considerable importance to accurately evaluate the highly-volatizing behavior of fission products (FPs) over multicomponent debris. Particularly, cesium (Cs)- and iodine (I)- bearing chemical species are regarded as notable FPs. In the present work, the authors have generated original thermodynamic databases for the system U–Zr–Ce–Cs–Fe–B–C–I–O–H featuring Cs- as well as I-bearing subsystems, which are contained in oxide, iodide, and metal (including borides and carbides) sub-databases. It has been confirmed that the phase diagrams calculated by the present set of the databases reproduce the corresponding literature data well in various kinds of subsystems of the above multicomponent system. The present set of databases has subsequently been applied to simulate phase equilibria and volatizing behavior of Cs- and I-including species, respectively, in multicomponent debris under specific temperature and atmospheric conditions corresponding to severe nuclear accidents.     

钯催化H2O2分解的机制探讨

高放废物（HLW）处置库近场地下水的辐解能够产生H₂O₂,其被裂变产物合金颗粒（ε-颗粒）的催化分解属于多相表界面反应。本工作选用钯粉模拟ε-颗粒,采用高压反应釜研究体系总压和H₂分压对反应的影响,并按一级动力学模型拟合实验数据。添加HO·的捕获剂和淬灭剂的实验证明无H₂反应过程中存在HO·的生成步骤。钯的催化活性及形态变化与反应时间的关系表明,产物氧吸附在钯的表面对反应具有毒化作用。通过持续监测滤液中H₂O₂浓度的变化,发现溶液中存在类似于Haber-Weiss的反应持续消耗H₂O₂。推导出钯对H₂O₂分解的机制过程和影响因素,为处置库的安全评估提供基础数据。     

Application of a boron doped diamond (BDD) electrode as an anode for the electrolytic reduction of UO2 in Li2O–LiCl–KCl molten salt

A boron doped diamond thin film electrode was employed as an inert anode to replace a platinum electrode in a conventional electrolytic reduction process for UO₂ reduction in Li₂O–LiCl molten salt at 650 °C. The molten salt was changed into Li₂O–LiCl–KCl to decrease the operation temperature to 550 °C at which the boron doped diamond was chemically stable. The potential for oxygen evolution on the boron doped diamond electrode was determined to be approximately 2.2 V vs. a Li–Pb reference electrode whereas that for Li deposition was around ?0.58 V. The density of the anodic current was low compared to that of the cathodic current. Thus the potential of the cathode might not reach the potential for Li deposition if the surface area of the cathode is too wide compared to that of the anode. Therefore, the ratio of the surface areas of the cathode and anode should be precisely controlled. Because the reduction of UO₂ is dependent on the reaction with Li, the deposition of Li is a prerequisite in the reduction process. In a consecutive reduction run, it was proved that the boron doped diamond could be employed as an inert anode.     

水-氢交换氢同位素体系HD/H_2O、DT/D_2O和HT/H_2O分离性能模拟研究

计算模拟应用于氢同位素分离领域,能够方便、快捷地进行工艺条件分析。本工作采用数值模拟的方法对比研究了水-氢催化交换过程中HD/H_2O、DT/D2O和HT/H_2O三种氢同位素体系的分离性能。研究表明:在一定工艺条件下,三种体系均在操作温度为343K时达到最大的分离效果;随着气液比从1.0增大到3.0,最优操作温度均从343K降低到323K,但是在此过程中,HT/H_2O体系的分离效果受温度的影响较小一些;在达到最大分离效果的目标下,HT/H_2O体系需要的理论塔板数比HD/H_2O和DT/D2O体系少,同时,在优化的工艺条件下,三体系气相中氢同位素浓度在交换柱内分布曲线存在一定的差异。     

分光光度法测定Gd2O3—UO2烧结芯块O／M的研究

分光光度法测定Ｇｄ２Ｏ３－ＵＯ２烧结芯块氧与金属原子比中，浓磷酸为溶剂，Ｕ＾６＋离子和Ｕ＾４＋离子的特征波长分别选为３１０ｎｍ和５４４ｎｍ。Ｕ＾６＋离子和Ｕ＾４＋离子浓度分别由其特征波长的吸光度值与标准曲线对比来确定。Ｏ／Ｍ计算公式由物质内部电中性原理导出。     

Simulation of multi-atomic interactions in H–O–W system with the MD code CADAC

For future tokamak reactors, chemical erosion of tungsten armour surfaces under impact of hot deuterium–tritium plasma that contains impurities, for instance oxygen, is an important issue. Oxygen can form volatile molecular complexes O_xW_y at the surface, and the retained H-atoms form the volatile complexes H_xO_y, which mitigates the erosion (H states for hydrogen isotopes). The plasma impact can substantially destroy the complexes.To describe this H–O–W system, the molecular dynamics (MD) code CADAC was earlier developed using only pair–atomic interactions. Now CADAC is extended for multi-body forces to simulate molecular organization of atoms near the tungsten surface. The approach uses the Abell's model of empirical bond-order potentials in addition combined, for the first time, with a valence concept. CADAC simulates chemical features using atomic valences and the Morse potentials. The new model is introduced and model parameters are estimated.     

联合电解催化交换系统HD／H2O和HT／H2O体系模拟

计入蒸汽的影响，研究建立基于两步传质的联合电解催化交换系统模型，计算HD／H2O和HT／H2O两个体系的分离性能。传质系数的提高能显著改善交换系统的整体性能，电解池浓缩倍数与电解池滞液量有关。电解池中氘浓度的增长最终将引起交换系统脱氘率的下降，这一现象表明，在交换系统操作模式选择以及与后级浓缩系统的级联匹配中，对交换系统的动态行为必须予以特别关注，并应在交换床设计中考虑此因素。