[ONSO]型Salen化合物的合成、单晶结构及金属离子识别

一些重金属离子即使在较低浓度时也会对环境、生物体产生毒性,所以研究痕量金属离子识别具有重大意义。荧光传感器由于具有选择性好、灵敏度高、成本低、实时响应等优点, 得到了广泛关注。以2,4-二叔丁基苯酚,3,5-二叔丁基水杨醛和邻氨基苯硫酚为原料合成了类Salen配体L1, 并用1H NMR,13C NMR,IR,元素分析及X射线单晶衍射等手段对其进行了表征。并通过自由挥发法得到了配体L1的单晶结构,实验表明L1是三斜晶、P-1空间群的一个空穴平面[ONSO]四配位环境。通过荧光光谱考察了类Salen配体与金属离子(Li+,Na+,K+,Cd2+,Cs+,Co2+,Cu2+,Hg2+,Mn2+,Ni2+,Zn2+,Ag+)的识别与配位性能。光谱滴定分析表明L1与Zn2+以1∶1的化学计量数配位。另外,L1与Zn2+结合后荧光显著增强,荧光检测限达到5.01×10-5 mol·L-1,而上述提到的其他常见金属离子不引起荧光光谱变化。结果表明L1是一个对检测Zn2+的选择性高,灵敏度强的荧光增强型探针。     

质子辐照不锈钢中氢气泡产生和演化研究

采用质子辐照模拟方法和正电子湮没寿命测量方法研究了质子辐照在国产改进型316L不锈钢中产生的氢气泡及其随辐照质子注量的演化过程。5×10^12,5×10^13,5×10^14／cm^2质子辐照的实验结果表明,辐照在不锈钢中产生氢气泡的尺度随辐照质子注量增加而增大,在质子注量为5×10^14／cm^2时氢气泡尺寸达到0．62nm,气泡的浓度随质子注量增加而减小。The bubble production and evolution in the home-made modified 316L stainless steel have been investigated by the proton irradiation simulation technique and the positron annihilation lifetime measurement. The experimental results of 5 × 10^12, 5 × 10^13 and 5 × 10^14/cm^2 proton irradiations show that the produced bubble size increases, while the bubble concentration decreases, with the increasing of the irradiation proton flueence. At the proton irradiation fluence of 5 × 10^14/cm^2 the bubble size reaches 0.62 nm.     

钨辐射损伤随辐照剂量变化的重离子辐照模拟研究

采用重离子辐照模拟方法和正电子湮没寿命测量技术研究了钨辐射损伤随辐照剂量的变化。20,60和90dpa（每个原子的位移次数）辐照损伤水平的实验结果表明,辐照在钨中产生单空位、双空位、位错和空位团等缺陷;随辐照剂量的增大,单空位、双空位和位错浓度增加,空位团的尺度和浓度都随之增大。Radiation damage in W has been studied as a function of irradiation dose by heavy ion simulation and positron annihilation lifetime measurement. The experimental results of 20, 60 and 90 dpa irradiations illustrate that the mono-and di-vacancies, dislocations and vacancy clusters are produced by the irradiation. The concentrations of the mono-and di-vacancies and dislocations and both the concentration and size of the vacancy clusters or voids all increase with the increasing of the irradiation dose.     

LaFeO3纳米材料电四极超精细相互作用TDPAC测量

用时间微分扰动角关联方法测量了LaFeO3纳米中的电四极超精细相互作用. 扰动角关联探针核14057La 14058Ce由139La(n,γ)140La反应产生, 实验只观察到一个La晶位的四极相互作用. 在室温下， 20和40 nm 以及晶体LaFeO3的四极相互作用频率ω0分别为 687.4 , 698.3 和742.9 Mrad/s , 频率分布宽度系数σ分别为 0.014, 0.009和0.001, 电场梯度不对称系数η=0. 实验数据表明, 电场梯度主轴与晶轴方向一致; 样品具有菱方结构, 晶体到纳米发生菱方向正交结构转变, 纳米尺度越小, 越趋于正交结构; 由于邻近核的扰动, 随纳米颗粒增大, 四极相互作用频率分布宽度系数σ变小, 晶体时最小. The quadrupole interactions in the nano and crystalline LaFeO3 perovskites have been investigated by TDPAC. The TDPAC probing nuclei 14057La 14058Ce were produced through the nuclear reaction 139La(n.γ)140La at the CIAE heavy water experimental reactor. One electric quadrupole interaction was detected for each material, which is assigned to the La site. The quadrupole interaction frequencies of 687.4, 698.3 and 742.9 Mrad/s with a distribution coefficient of 0.014, 0.009 and 0.001 were observed at room temperature for the 20 and 40 nm nano LaFeO3 and crystalline LaFeO3, respectively. The fitting yielded the EFG asymmetry parameter η=0, which indicates that the principal axes of the EFG is aligned with the crystallographic axes. The experimental results show that the structure of crystalline LaFeO3 is rhombohedral, the changing of the structure towards the orthorhombic structure takes place from the crystalline LaFeO3 to the nano LaFeO3, and the smaller the nano grain size, the larger the change. The frequency distribution is caused by the perturbation of the neighboring atoms, and thus, the distribution coefficient increases with decreasing the nano grain size and the crystalline LaFeO3 arrives at its maximum.     

PdAgHx金属氢化物正电子湮没研究

在77—295 K温区和氢浓度0—0.35范围采用正电子湮没寿命测量方法研究了Pd0.75Ag0.25H_x氢化物合金. 充氢后正电子湮没寿命谱可以用两个寿命成分表征. 短寿命成分τ1不随温度和氢浓度变化, 是自由正电子湮没寿命; 长寿命成分τ2及其相对强度I2不随温度变化, 但随氢浓度的增加分别增大和减小, τ2是氢气泡捕获的正电子湮没寿命, τ2增大和I2减小说明随氢浓度增大氢聚集成的气泡的尺度增大, 而浓度减小. 实验结果表明, 氢脆的微观机理是氢气泡致脆. The metal hydride PdAgHx with a hydrogen concentration x ranging from 0 to 0.35 has been investigated by positron annihilation lifetime method in the temperature region between 77 K and 295 K. The measured lifetime spectra in metal hydride PdAgHx are characterized by two lifetimes τ1 and τ2. The short lifetime τ1 is independent of both hydrogen concentration and temperature, which is ascribed to the annihilation lifetime of free positrons. The long lifetime τ2 and its intensity I2 do not change with temperature, while τ2 increases and I2 decreases with increasing of hydrogen concentration. τ2 is attributed to the lifetime of positrons trapped at the hydrogen bubble. The increase of τ2 indicates the growth of the hydrogen bubble, and the decrease of I2 shows the reduction of the hydrogen bubble concentration. The experimental result shows a microscopic mechanism that the hydrogen bubble produced causes hydrogen embrittlement.     

南京地区实际气溶胶对臭氧探测的影响

本文研究了在实测的南京地区五种气溶胶分布下,大气气溶胶对三波长差分吸收激光雷达(Dual-DIAL)臭氧探测结果的影响,使用波长对266nm,289nm,308nm进行了误差分析。通过对实际气溶胶的误差分析,模拟出在大部分高度上误差最小的C值(为消去后向散射及消光项误差引入的比值)C=1.7,并与传统方法取得的C=23/19进行了对比。讨论了气溶胶分布及含量对C值选取的影响及不同C值下误差随气溶胶变化的规律;分析得出对于本文所使用的气溶胶分布以及波长对,取C=1.7时在气溶胶较均匀时误差接近于零,误差不会大于5%,当气溶胶变化率变高且频繁变化时误差最大可达40%。取C=23/19时误差很稳定,不随气溶胶分布变化,误差高度增加误差减小且小于10%。本文还讨论了不同气溶胶分布下C的选取方法。