Investigation of the Rb-W-O system in connexion with the superconducting properties of the hexagonal tungsten bronzes

The previous studies of the superconducting properties of the hexagonal tungsten bronzes have repeatedly come up against the lack of reproducibility of the data and, at the first place, of the data relating to the stability of superconducting state. We revisited this problem and identified the main causes of these contradictory data in Rb_xWO₃, among which the major one is the ordering of the alkali atoms. Our study has emerged onto a determination of the x dependence of the order-disorder transition, of the lattice parameters and of the superconducting transition temperature T_c. We have also clarified the crystal structure and examined the mechanisms involved in the oxidation and reduction of this compound. Finally, we have assembled our data to draw a plausible Rb-W-O phase diagram.     

新干商墓青铜器非晶与纳米晶锈蚀产物结构的分析研究

应用微区X射线衍射仪(μXRD)及高分辨透射电镜(HTEM)分析江西新干商墓出土的青铜器粉状锈蚀产物,结果表明锈蚀产物主要为具有锡石结构的SnO2,晶态形式为非晶与晶粒尺寸为4～5.7nm的纳米晶共混;能谱分析表明样品中除含有大量锡外,还有少量的铜、硅、铅与铁等元素。通过对锈蚀产物的高分辨透射电镜晶格条纹像计算,说明纳米晶SnO2的晶格中并没有其他原子的掺杂;对该锈蚀产物拉曼光谱的分析研究表明,样品不含有表征SnO2的体相拉曼峰,更具有非晶SnO2的特征,而973cm-1的弱而宽的峰表明样品含有非晶的硅酸盐类的锈蚀物,推测锈蚀产物中的少量铜、硅、铅与铁等元素应以非晶的形式存在。     

The influence of the lithium concentration on the low-temperature phase transition in phases LixV2O5 with shcherbinaite-structure

With high-resolution Guinier diffractometry the low-temperature stability of the intercalated lithium vanadium oxide bronzes ε - Li _x V₂O₅, with 0.32 ≤ x ≤ 0.80, was studied. In the course of these investigations a line of thermally induced structural phase transitions was detected in the x-T field. The reversible continuous phase transitions can be described in terms of a classical Landau-type theory. They are proper (potentially) ferroelastic with an one-dimensional order parameter transforming as the Γ⁺ ₃ irreducible representation of space group Pmmn. The symmetry is orthorhombic P2₁/m2₁/m2/n above T_c , but monoclinic P2₁ /m11 below T_c .

The transition temperatures depend strongly on the stoichiometry of the intercalated lithium ions. The critical exponent β, and, hence, the character of the phase transition do not change significantly with the lithium concentration. However, for x ≤ 0.52 corresponding phase transitions could not be detected, supporting the idea that the accepted stability field of ε - Li _x V₂O₅(0.32 ≤ x ≤ 0.80) should be subdivided into two fields, ε- and ε'-phase, according to whether the phase transition occurs, or not. The influence of the reduction rate of the intercalated phases on the critical parameters will be discussed in terms of a mean-field theory.     

热分析法测定非计量化合物NaxWO3的组成

Na_xWO₃是1种非计量化合物(0xWO₃中的W处于W(Ⅴ)和W(Ⅵ)₂种不同的价态。     

The potential of laser-induced breakdown spectrometry for real time monitoring the laser cleaning of archaeometallurgical objects

In this work, an orthogonal double pulse (DP) laser-induced breakdown spectroscopy configuration as a diagnostic tool for the restoration of archaeometallurgical samples has been developed and evaluated. Although laser-induced breakdown spectroscopy has been extensively tested in this kind of applications, this study presents an alternative method in terms of controlling the laser cleaning process of metallic object as well as real time laser-induced breakdown spectroscopy monitoring of the emission signal of the ablated material (pollutants and the structural materials). Several experimental parameters such as interpulses delay time, second laser to target distance and second pulse energy delay have also been accomplished in ancient Alexandrian coins. An enhancement of the signal emission is observed when both cleaning and analyzing lasers are combined, while no spectra signal is achieved when both lasers are operating independently. The restoration of ancient object by means of both conventional and double pulse laser cleaning arrangements is also discussed.