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     

What Is Its Real Existing Form?——Theoretical and Experimental Studies on 2-Mercaptobenzothiazole

1 INTRODUCTION The study of heterocyclic molecules with aroma- tic rings and their absorptions on metals is of con- siderable importance from both theoretical and te- chnological points of view. These molecules are in- teresting because of their applications as corrosion inhibitors and flotation collectors, and their abilities to form self-assembly layers[1]. 2-Mercaptobenzo- thiazole (C7H5NS2, in the following MBT) is an important heterocyclic molecule, which can be used as corrosion …     

Preparation, structure and properties of novel 1,3-dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units

1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts.     

An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

Effect of induced shielding current transmission in longitudinal direction on levitation force of melt grown single-domain YBa_2Cu_3O_(7-x) cylindrical superconductor

YBa2Cu3O7-x (YBCO) bulk is one of the most important high temperature superconducting materials for magnetic levitation applications, because it has a high magnetic irreversibility field Hirr at liquid nitrogen temperature, and can grow into large grains. The levitation force of YBCO bulk is proportional to the critical current density (Jc) and grain radius (r)[1], so higher Jc and r are appreciated for YBCO bulks to achieve higher levitation force. Now single-domain YBCO bulks up to s…     

Hydrothermal Synthesis and Structure of [Mn(C_8H_5NO_4)·H_2O]_n·2nH_2O

1 INTRODUCTION The self-assembly of organic-inorganic hybrid ma- terials is an intriguing area, which is yielding new generations of supramolecular architectures[1, 2]. Coor- dination by transition metals with multifunctional ligands is one of the main design principles. As a rigid multi-dentate ligand, 5-aminoisophthalic acid (AIP) has received considerable attention owing to the variety of bridging abilities[3~8]. It can engage in three types of intermolecular interactions: (1) M-L b…     

Crystallographic report: Bis{[diacetyl‐bis(2,6‐isopropylphenylimine)]nickel(I)(µ‐chloro)}

The first α‐diimine nickel(I) complex having a chloro bridge is reported. The centrosymmetric dinuclear structure of {[ArN?C(Me)C(Me)?NAr]NiCl}₂[Ar?2,6?C₆H₃(i‐Pr)₂] features two chelating α‐diimine ligands and two bridged chlorine atoms, so that a distorted tetrahedral N₂Cl₂ coordination geometry for nickel results. Copyright © 2004 John Wiley & Sons, Ltd.     

Crystallographic report: A new polymorph for bis[bis(N,N‐dibenzyldithiocarbamato)cadmium(II)]

The title compound is a centrosymmetric dimer with each cadmium in a distorted CdS₅ square pyramidal geometry. The Cd–S bond distances range from 2.5626(11) to 2.8459(11) Å. Copyright © 2004 John Wiley & Sons, Ltd.