铀在Nd_2Zr_2O_7烧绿石中的固溶量及重离子辐照效应

Nd_2Zr_2O_7烧绿石因其稳定的物理化学性质和辐照稳定性可以作为高放废物中锕系核素的固化基材.通过溶胶凝胶—喷雾热解—高温烧结方法制备了含铀的Nd_2Zr_2O_7烧绿石固化体;开展了Nd_2Zr_2O_7和Nd_(1.9)U_(0.1)Zr_2O_7固化体的重离子辐照实验,辐照剂量为1 dpa和3 dpa;利用X射线衍射和Raman光谱对固化体结构进行了分析.研究发现铀在Nd_2Zr_2O_7烧绿石体系的固溶量仅为10 at%,高价态铀掺杂导致固化体结构向无序化转变.重离子辐照实验表明, Nd_2Zr_2O_7烧绿石基材具有较高的抗辐照稳定性;而Nd_(1.9)U_(0.1)Zr_2O_7在较低辐照剂量下,固化体烧绿石体系结构破坏,重离子辐照诱导固化体结构转变为更加无序化的萤石结构.低固溶量和抗辐照能力减弱主要是由于锕系核素烧绿石固化体的结构无序化所致.     

U：CaF2晶体的分凝特性与光谱性质

应用TGT法生长了直径为75mm的U：CaF2晶体，宏观上透明完整.应用公式K0=Cs/Cl计算了U在CaF2晶体中的分凝系数等于0.53.应用溶质分布一般公式Cs=K0C0(1-g)K0-1，计算U的浓度分布与测量值，数值符合说明晶体生长过程接近平衡状态.分析不同条件下生长的U: CaF2晶体的晶胞参数和吸收光谱，结果表明生长气氛决定U的价态及电荷补偿机理：无PbF2存在的条件下，U为+4价，晶体呈绿色；PbF2的加入起到氟化去氧作用，U倾向于以离子半径最接近于Ca2+的U3+存在，晶体呈红色.从晶体生长开始到结束的部位，U3+:CaF2晶体吸收光谱的峰位不变，峰强呈现与U浓度相同的增加趋势.U3+:CaF2晶体外层厚约5mm处呈黄色，含有U3+和U2+的混合价态离子，其原理是石墨坩埚的还原作用通过单质铅，使部分的U3+进一步还原成了U2+. 关键词： 铀 氟化钙晶体 分凝系数 晶胞参数     

高温超导体环流演示仪

利用永磁铁对超导样品进行激励,产生的超导环流不衰减,由此原理制做了高温超导环流演示仪,该仪器可演示零电阻现象、环流磁场及超导体电阻与温度的关系.     

Photoconversion and photocatalytic activity of uranyl in acetone solutions

We have studied the effect of irradiation on the uranyl nitrate — acetone and uranyl perchlorate — acetone systems. We have established that when the uranyl perchlorate — acetone system is irradiated, polymerization of the acetone occurs and the catalyst for the process is excited uranyl complexes. In the polymer, uranium is found in the form of nanoclusters of pentavalent and tetravalent uranium, formed as a result of photochemical reactions. Polymerization does not occur in the uranyl nitrate — acetone system. We consider possible factors responsible for the noted differences. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 565–568, September–October, 2007.     

Binuclear Uranium(VI) Complexes with a “Pacman” Expanded Porphyrin: Computational Evidence for Highly Unusual Bis‐Actinyl Structures

On the basis of uranyl complexes reacting with a polypyrrolic ligand (H₄L), we explored structures and reaction energies of a series of new binuclear uranium(VI) complexes using relativistic density functional theory. Full geometry optimizations on [(UO₂)₂(L)], in which two uranyl groups were initially placed into the pacman ligand cavity, led to two minimum‐energy structures. These complexes with cation–cation interactions (CCI) exhibit unusual coordination modes of uranyls: one is a T‐shaped ( T ) skeleton formed by two linear uranyls {O_exo?U₂?O_endo→U₁(?O_exo)₂}, and another is a butterfly‐like ( B ) unit with one linear uranyl coordinating side‐by‐side to a second cis‐uranyl. The CCI in T was confirmed by the calculated longest distance and lowest stretching vibrational frequency of U₂?O_endo among the four U?O bonds. Isomer B is more stable than T , for which experimental tetrameric analogues are known. The formation of B and T complexes from the mononuclear [(UO₂)(H₂L)(thf)] ( M ) was found to be endothermic. The further protonation and dehydration of B and T are thermodynamically favorable. As a possible product, we have found a trianglelike binuclear uranium(VI) complex having a O?U?O?U?O unit.     

自然循环过冷沸腾流动不稳定性的实验研究

本文以氟里昂作工质，对自然循环过冷沸腾流动不稳定性进行了实验研究．实验过程中发现自然循环系统内可能发生高频脉动和低频脉动二种类型的过冷沸腾流动不稳定性．通过实验研究揭示了这二种类型流动不稳定性的发生机理，证实高频脉动属于声波型脉动，低频脉动属于密度波型脉动．通过实验得出了判断系统稳定性的界限，并使用积分方程无因次分析方法得出了预测密度波型流动不稳定性的经验公式．     

Infrared spectra and structure of tetravalent uranium chloride nanoclusters in electron-donor solvents

We have studied the IR absorption spectra of tetravalent uranium chlorides in electron-donor solvents. We discuss the changes in these spectra on coordination of the solvent molecules to the tetravalent uranium. We consider the participation of water molecules in this process. On this basis, we draw the conclusion that clusters form with coordination number equal mainly to six. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 729–732, September–October, 2008.     

海气相互作用的若干时频特征

本文利用交叉谱分析方法分析了北大西洋、北太平洋以及印度洋六个海区与500百帕四个大气活动区之间的关系,揭示了它们之间的时空特点.进而分析了中低纬度海气相互作用的时频特点,并对三大洋副热带高压之间的相互关系进行了讨论,得到了一些有意叉的结果.这给利用海气关系进行长期天气过程分析提供了可靠依据。