UO_2(NO_3)_2-U(NO_3)_4-HNO_3/30%TBP-煤油体系萃取平衡分配数据的测定

在下列条件下,系统地测定了U(VI)-U(IV)-HNO_3/30% TBP-煤油体系中各溶质的萃取平衡数据187组。条件为:25±0.5℃;原始水相中U(IV)浓度为5—50g/l;U(VI)浓度为15—150 g/l;肼浓度为0.1mol/l; HNO_3 0.4—4 mol/l。经物料衡算检验,数据基本可靠,可用于萃取平衡的数学描述。     

U(Ⅵ)电还原反萃动力学研究——Ⅱ.U(Ⅵ)反萃和U(Ⅳ)萃取动力学

本文在带有阴阳极的恒界面池中研究了HNO_3-N_2H_5NO_3(H_2O)/UO_2(NO_3)_2-HNO_3(30％TBP-煤油)体系在U(Ⅵ)电解还原过程中的U(Ⅵ)反萃和U(Ⅳ)萃取动力学。这是U(Ⅵ)电还原反萃动力学研究的第二步。根据实验结果和数据处理,得到U(Ⅵ)反萃和U(Ⅳ)萃取过程的表观活化能分别为36.02kJ/mol和21.13kJ/mol;U(Ⅵ)反萃和U(Ⅳ)萃取速率随两相搅拌速率的增大而增大;U(Ⅵ)反萃和U(Ⅳ)萃取过程均由扩散控制。随着阴极电位的降低,U(Ⅵ)反萃和U(Ⅳ)萃取速率均增大。     

NpO2+与UO22+阳阳离子络合对30%TBP-煤油萃取Np(Ⅴ)性能的影响

通过分光光度法和液闪计数法研究了Np(Ⅴ)与U(Ⅵ)间的阳阳离子络合作用对Np(Ⅴ)在30%TBP-煤油有机相中的萃取分配行为的影响。结果表明：Np(Ⅴ)-U(Ⅵ)阳阳离子络合物可被萃入TBP有机相中，其萃取分配系数较Np(Ⅴ)提高了数倍。随着U浓度在0.12～0.60 mol/L范围内升高，Np(Ⅴ)-U(Ⅵ)阳阳离子络合物萃取分配系数不断增加，当U浓度达到0.72 mol/L时，由于有机相铀饱和度原因，Np(Ⅴ)-U(Ⅵ)阳阳离子络合物萃取分配系数下降。在室温下，水相酸度为3 mol/L、铀浓度为0.60 mol/L、相比（o/a）为2∶1、两相接触时间为1 min时，Np(Ⅴ)的总萃取分配系数约为0.1，萃入有机相中的Np约占Np总量的9%。提高酸度有利于Np(Ⅴ)-U(Ⅵ)阳阳离子络合物的萃取，接触时间在1～8min范围内对萃取无影响。     

铀酰离子光化学研究 Ⅲ.Ar~ 激光对UO_2(NO_3)_2-HCOOH-HNO_3体系U(Ⅵ)的光化学还原

用Ar~ 激光器的4880A单色光较详细地研究了UO_2(NO_3)_2)-HCOOH-HNO_3水溶液体系中UO_3~(2 )的光化学行为。结果表明,在此体系中吸收光物质主要是甲酸铀酰络合物,甲酸铀酰络合物首先还原生成U(Ⅴ),随后歧化生成U(Ⅳ)、U(Ⅵ)。生成U(Ⅳ)的量子产额Φ主要取决于溶液中甲酸铀酰络合物的生成度α。温度升高,Φ先是增大,而后降低。在低浓度范围,U(Ⅳ)生成速率分别与UO_2~(2 )浓度或HCOO-浓度成正比。所假设的反应机理能较好地符合一些实验结果。     

肼为还原剂催化还原U(Ⅵ)制备U(Ⅳ)的工艺条件

研究了硝酸体系中以铂黑为催化剂、肼为还原剂还原制备U(Ⅳ)的工艺条件,考察了硝酸浓度、肼浓度、反应温度、催化剂用量等对U(Ⅵ)转化率及副反应的影响。当铀浓度为0.90mol/L时,优化的工艺条件为：初始硝酸浓度0.80mol/L,初始肼浓度1.0mol/L左右,反应温度60℃,反应液25mL时催化剂铂黑用量为0.2g,反应3h后U(Ⅵ)的转化率大于99%。     

磷酸三异戊酯、磷酸三仲丁酯对U(Ⅵ)、Th(Ⅳ)的萃取性能

研究了磷酸三异戊酯(TiAP)、磷酸三仲丁酯(TsBP)的正十二烷溶液从硝酸介质中萃取U(Ⅵ)、Th(Ⅳ)的性能及Th(Ⅳ)的萃取容量,并在相同条件下与磷酸三丁酯(TBP)的萃取性质进行了比较。结果表明:TiAP对Th(Ⅳ)、U(Ⅵ)的萃取性能与TBP相近,相同酸度情况下,分配比均略高于TBP;TsBP萃取U(Ⅵ)的分配比高于TBP,而萃取Th(Ⅳ)的分配比低于TBP。随着水相硝酸浓度的增大,两种萃取剂对Th(Ⅳ)、U(Ⅵ)的萃取分配比增大,但在较高酸度下则相反;同时比较了TiAP、TsBP、TBP对Th(Ⅳ)的萃取容量。     

U(Ⅲ)-U(Ⅳ)同位素交换过程的同位素效应

本文研究了U(Ⅲ)-U(Ⅳ)在7.0mol/l HCl介质中及在U(Ⅲ)-7.0mol/l HCI-U(Ⅳ)-50％TBP-煤油和U(Ⅲ)-7.0mol/l HCl-U(Ⅳ)-50％TBP-二甲苯体系中的同位素交换过程,测得上述体系的单级分离因数分别为1.0026,1.0031和1.0030,从而证实了P.Delvalle的1.0025-1.0030的实验结果;确认了用液态Zn-Hg齐制备U(Ⅲ)是快速、有效的方法;初步探索了用U(Ⅲ)-U(Ⅳ)交换过程浓缩~(235)U的合适体系。     

U(Ⅳ)用作Purex过程中Pu(Ⅳ)还原剂的研究

研究了U(Ⅳ)在分离的有机相(30％TBP-煤油)中、在两相振荡混合和逆流萃取过程中的稳定性。通过单级反萃实验研究了有机相中钚浓度、铀浓度,反萃剂的酸度和肼浓度,U(Ⅳ)用量(M_(u(Ⅳ))/M_(Pu)对钚反萃率的影响。通过串级实验研究了在1B槽工艺条件下,M_(u(Ⅳ))/M_(Pu)和U(Ⅳ)加入位置,反萃剂酸度和相比等条件的变化对铀钚分离的影响。给出了铀和钚的净化系数。     

UO_2(NO_3)_2-HNO_3-N_2H_5NO_3(H_2O)/30%TBP(煤油)体系中组分浓度对U(Ⅵ)电解还原速率影响的研究

本文在振动搅拌槽中,研究了UO_2(NO_3)_2-HNO_3-N_2H_5NO_3(H_2O)/30％TBP(煤油)体系的水相电解液组分浓度对U(Ⅵ)电解还原速率的影响。根据实验所得数据,经回归分析得到反应动力学微分方程 式中速度常数k一般说是温度的函数。25℃时,k=0.00187。在实验浓度范围内,U(Ⅵ)还原速率随U(Ⅵ)浓度升高而增大,表观反应级数为0.75级;而[N_2H_5~+]及[HNO_3]影响不大,反应级数近于0。     

在TBP-煤油有机相中光化还原制取U(Ⅳ)的研究——Ⅱ.降解产物的产生和它们对萃取的影响

本文研究了在TBP-煤油体系中光化还原制取U(Ⅳ)时,降解产物的产生和它们对萃取性能的影响。结果表明,TBP-煤油的主要降解产物有DBP和MBP、羰基化合物和硝基烷。光照后的有机相经稀酸反萃和碱洗所得回收萃取剂的萃铀分配比、铀保留值和分相时间与新鲜萃取剂无明显差别)。     

Vaporization and Surface Ionization of LaC2, CeC2, PrC2, NdC2, ThC2 and UC2

The Langmuir vaporization and the surface ionization of LaC₂, CeC₂, PrC₂, NdC₂, ThC₂ and UC₂ from a heated graphite filament have been studied mass spectrometrically. It was found that there were present small amounts of neutral and ionic metal dicarbide molecules in addition to neutral and ionic metal atoms in the LaC₂, CeC₂, PrC₂, ThC₂ and UC₂-C systems with the exception of NdC₂-C, where neither neutral nor ionic metal dicarbide molecules were observed. The reason for this exceptional behavior of the NdC₂-C system is explained by the very small vaporization coefficients, as estimated from the measurements of neutral MC₂/M ratios and ionic MC₂/M ratios.

From the measurements of the heats of vaporization, it was surmised that the ionization potential of Th measured by the surface ionization comparison technique might be too high.     

Vapor Species over Na2O-B2O3-SiO2-Cs2O Glass

Methods for suppression and control of the axisymmetric vertical positional instability are described on the basis of conceptural design studies with the International Tokamak Reactor (INTOR). The shell effect is well known to be useful for suppression of the fast instability. Here shell structures are presented and their usefulness is assessed. Included in the assessments are required modellings of the plasma current for determination of mutual inductances between the plasma and the inductive components around it. Three kinds of models are described and their features are compared to the shell effect. Two kinds of simplified reactor structures are described and studied by comparing them with some control characteristics of the slow instability by a pair of control coils. Their structures are selected so as to result in different shell effects between them, and are consequently found to produce different capacities of power supply, too.     

Ternary Compounds PuNiC2 and PuCoC2

In order to determine a crack propagation rate of less than 10^-8 mm/s in a 24-hour integrated measurement, major parameters of a coupled system of a constant tension specimen and crack depth measurement, based on potential drop method, have been optimized. Influences of sensor geometry, location for detecting potential drop and data processing of the ratio of signal to noise (S/N) were optimized by applying Taguchi's Method. Then a suitable sensor geometry and data processing method were proposed to get a robust measurement system with higher sensitivity and lower susceptibility for geometrical and procedural fluctuations.

By applying the optimal crack propagation rate measurement system, it was confirmed that a crack propagation rate of lxlO^-8 mm/s can be measured under a low concentration condition of hydrogen peroxide with less than a 20% error by a 24-hour integrated measurement.     

纳米SnO2和SnO2／SiO2材料的正电子湮没研究

采用溶胶一凝胶法制备了纯纳米ＳｎＯ２和掺杂ＳｉＯ２的纳米ＳｎＯ２材料，应用Ｘ射线衍射和正电子湮没寿命谱等手段进行了纳米材料的界面结构和纳米晶粒的生长过程，结果表明，所制备的纳米ＳｎＯ２和ＳｎＯ２／ＳｉＯ２材料中只存在两类缺陷，分别对短寿命τ１和中等寿命τ２，材料中两类缺陷的数量比与粒径有关，纳米ＳｎＯ２晶粒生长随热处理温度升高为分两个阶段，低于晶化临界温度时，晶粒生长缓慢，高于此温度时，则生长迅速     

Study on Redox Equilibrium of UO2 2+/U2 + in Molten NaCl-2CsCl by UV-Vis Spectrophotometry

In order to enhance the understanding of the redox equilibriums of uranyl ions in molten NaCl-2CsCl eutectic salt UV-Vis absorption spectrophotometry measurements were performed for UO₂ ²⁺ in molten NaCl-2CsCl at 923 K under simultaneous electrolytic control of their ratio. A prominent absorption band at 395 nm was assigned to UO₂ ⁺, and its molar absorptivity was determined to be 832±27 mol^-1·l·cm^-1. From the dependence of the rest potential of the melt on the spectrophotometrically determined ratio of [UO₂ ²⁺]/[UO₂ ⁺], the standard redox potential of the couple UO₂ ²⁺/UO₂ ⁺ was determined to be ?0.903±0.007 V vs. Cl₂/Cl^—.