In order to understand the effect of surface chemical groups on the immobilized species, Au-containing imidazolium-based ionic liquid (IL) [Bmim][AuCl4] was intentionally immobilized on polystyrene (PS) submicrospheres (d～300 nm) with a very small surface area (4-10 m2/g), which possess carboxyl-moiety (COONa or COOH) on the surface. The behavior of immobilized [Bmim][AuCl4 ] on the two types of submicrospheres was investigated by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and powder X-ray diffraction (XRD). It was revealed that the melting points (Tm) of [Bmim][AuCl4 ] that had been immobilized on PS-COONa and PS-COOH submicrospheres were decreased by 2.7 and 4.1℃, respectively. The interaction mechanism between the IL and submicrosphere surface moieties was further analyzed by X-ray absorption fine structure (XAFS) analysis. The data indicated that the coordination environment of Au species changed markedly when [Bmim] [AuCl4] was immobilized on the surfaces of PS-COONa and PS-COOH submicrospheres, as illustrated by the decrease in white line peak intensity. The effect of surface COOH groups on Tm depression and the white line peak intensity of the XANES spectrum is more pronounced than that of COONa groups, most likely due to the possible hydrogen bond formation between the COOH group and [Bmim]+.
HE YaXingFU HaiYingLI ChengJI XiangGE XueWuZOU YangJIANG ZhengXU HongJieWU GuoZhong
Copper ion is the essential microelement to many organisms. In this paper, the local structure of Cu2+ in CuBr2 aqueous solutions with different concentrations are investigated by using X-ray absorption fine structure (XAFS) technique. XANES (X-ray Absorption Near Edge Structure) spectra indicate that charge transfer from Br- to Cu2+ decreases with the solution concentration, which lead to a shift of the absorption edge. The shoulder appearing at the rising edge proves to be characteristic of a tetragonal distortion. The Fourier transform magnitudes of EXAFS (Extended X-ray absorption fine structure) data of Cu species suggest that more Cu-Br bonds may exist in high concentrations. A fivefold coordination configuration like a pyramid is used as the fitting parameters. From the analysis of the coordination numbers, the proportion of Cu-O and Cu-Br is 4:1 in the saturated solution. The Br atom is on the equatorial plane of the model. The fitting results agree well with the experiment data.
DAI Binbin WANG Qian MA Jingyuan LI Jiong ZHANG Shuo HUANG Yuying HUANG Wei WU Guozhong ZOU Yang JIANG Zheng XU Hongjie
氟盐冷却球床高温反应堆(Pebble Fluoride-Salt-Cooled High Temperature Reactors,PB-FHR)的冷却剂温度反应性系数与其堆芯活性区的几何尺寸有直接关系,研究选取7Li摩尔含量为99.995%的2Li F-Be F2做冷却剂,对冷却剂温度反应性系数与PB-FHR的堆芯活性区体积的关系进行定量分析。利用SCALE5.1软件对不同堆芯活性区体积的PB-FHR的冷却剂温度反应性系数进行了研究。分析结果表明:堆芯活性区体积越大的PB-FHR,冷却剂温度反应性系数越趋于正值,堆芯活性区体积越小的PB-FHR,冷却剂温度反应性系数越趋于负值。基于四因子公式的分析表明,逃脱共振俘获的概率、不泄漏概率和热中子利用系数在不同堆芯活性区体积的PB-FHR内的差异是影响冷却剂温度反应性系数差异的主要原因。
Nb can improve the resistance of Ni-based Hastelloy N alloy to Te-induced intergranular embrittlement.First-principles calculations are performed to research this mechanism by simulating the Ni(111) surface and the 5(012) grain boundary. The calculated adsorption energy suggests that Te atoms prefer diffusing along the grain boundary to forming the surface-reaction layer with Nb on surface of the Ni alloy. First-principles tensile tests show that the Nb segregation can enhance the cohesion of grain boundary. The strong Nb-Ni bonding can prevent the Te migration into the inside of the alloy. According to the Rice-Wang model, the strengthening/embrittling energies of Nb and Te are calculated, along with their mechanical and chemical components.The chemical bonds and electronic structures are analyzed to uncover the physical origin of the different effects of Te and Nb. Our work sheds lights on the effect of Nb additive on the Te-induced intergranular embrittlement in Hastelloy N alloy on the atomic and electronic level.
