Structural disorder in Ba0.6Sr0.4Al2O4

The structural disorder in Ba_0.6Sr_0.4Al₂O₄ (space group P6₃22) was investigated by X-ray powder diffraction and selected-area electron diffraction (SAED). The initial structural model was determined using direct methods, and it was further modified by the combined use of Rietveld method and maximum-entropy method (MEM). MEM-based pattern fitting method was subsequently applied, resulting in the final reliability indices of R_wp=9.61%, R_p=6.96%, R_B=1.40% and S=1.25. The electron density distribution was satisfactorily expressed by the split-atom model in which the strontium/barium and oxygen atoms were split to occupy the lower symmetry sites. The diffuse scattering in SAED was mainly attributable to the positional disorder of oxygen atoms.     

Zum Reaktionsverhalten der Tris(dialkylthiophosphinyl)phosphane – Die Kristallstruktur von [Ag{O[P(S)Me2]2}2] [AsF6]

Reactivity of Tris(dialkylthiophosphinyl)phosphines – Crystal Structure of [Ag{O[P(S)Me₂]₂}₂][AsF₆] In contrast to tris(dialkylphosphoryl)phosphines the reaction of tris(dimethylthiophosphinyl)phosphine with transition metal hexafluoroarsenates of the type [M(SO₂)_m [AsF₆]_n (M = Ag, m = 0, n = 1; M = Fe, Cd, m = n = 2) forms no molecular 2 : 1-complexes but polymeric products. The silver polymer is transformed into [Ag{O[P(S)Me₂]₂}₂][AsF₆], which is also formed by the reaction of Ag[AsF₆] with O[P(S)Me₂]₂. It crystallizes in the space group P1 with a = 862.5(2), b = 1 241.4(2), c = 1 254.0(3)pm, α = 80.34(1), β = 101.99(6), γ= 73.75(1)° (at 20°C) and Z = 2. The central silver atom is surrounded by four sulphur atoms in a slighly distorted tetrahedron. The average (Ag? S) and (P? S) bond lengthes are 259.4(2) pm and 194.9(2)pm, respectively.     

From Weakly Coordinating to Non‐Coordinating Anions? A Simple Preparation of the Silver Salt of the Least Coordinating Anion and Its Application To Determine the Ground State Structure of the Ag(η2‐P4)2+ Cation

The unexpected but facile preparation of the silver salt of the least coordinating [(RO)₃Al‐F‐Al(OR)₃]^? anion (R=C(CF₃)₃) by reaction of Ag[Al(OR)₄] with one equivalent of PCl₃ is described. The mechanism of the formation of Ag[(RO)₃Al‐F‐Al(OR)₃] is explained based on the available experimental data as well as on quantum chemical calculations with the inclusion of entropy and COSMO solvation enthalpies. The crystal structures of (RO)₃Al←OC₄H₈, Cs⁺[(RO)₂(Me)Al‐F‐Al(Me)(OR)₂]^?, Ag(CH₂Cl₂)₃⁺[(RO)₃Al‐F‐Al(OR)₃]^? and Ag(η²‐P₄)₂⁺[(RO)₃Al‐F‐Al(OR)₃]^? are described. From the collected data it will be shown that the [(RO)₃Al‐F‐Al(OR)₃]^? anion is the least coordinating anion currently known. With respect to the fluoride ion affinity of two parent Lewis acids Al(OR)₃ of 685 kJ mol^?1, the ligand affinity (441 kJ mol^?1), the proton and copper decomposition reactions (?983 and ?297 kJ mol^?1) as well as HOMO level and HOMO–LUMO gap and in comparison with [Sb₄F₂₁]^?, [Sb(OTeF₅)₆]^?, [Al(OR)₄]^? as well as [B(R^F)₄]^? (R^F=CF₃ or C₆F₅) the [(RO)₃Al‐F‐Al(OR)₃]^? anion is among the best weakly coordinating anions (WCAs) according to each value. In contrast to most of the other cited anions, the [(RO)₃Al‐F‐Al(OR)₃] anion is available by a simple preparation in conventional inorganic laboratories. The least coordinating character of this anion was employed to clarify the question of the ground state geometry of the Ag(η²‐P₄)₂⁺ cation (D_2h, D₂ or D_2d?). In agreement with computational data and NMR spectra it could be shown that the rotation along the Ag‐(P‐P‐centroid) vector has no barrier and that the structure adopted in the solid state depends on packing effects which lead to an almost D_2h symmetric Ag(η²‐P₄)₂⁺ cation (0 to 10.6° torsion) for the more symmetrical [Al(OR)₄]^? anion, but to a D₂ symmetric Ag(η²‐P₄)₂⁺ cation with a 44° twist angle of the two AgP₂ planes for the less symmetrical [(RO)₃Al‐F‐Al(OR)₃]^? anion. This implies that silver back bonding, suggested by quantum chemical population analyses to be of importance, is only weak.     

Synthesis, characterization and thermal properties of small R2R2NX-type quaternary ammonium halides

Twenty-one R₂R^′₂N⁺X⁻ -type (R=methyl or ethyl, R^′=alkyl, X=Br or I) quaternary ammonium (QA) halides have been prepared by using a novel one-pot synthetic route in which a formamide (dimethyl-, diethylformamide, etc.) is treated with alkyl halide in the presence of sodium or potassium carbonate. The formation of QA halides was verified with ¹H-NMR, ¹³C-NMR, MS and elemental analysis. The crystal structures of four QA halides (two bromide and two iodide) were determined using X-ray single crystal diffraction, and the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. The thermal properties of all compounds were studied using TG/DTA and DSC methods. The smallest compounds decomposed during or before melting. The decreasing trend of melting points was observed when the alkyl chain length was increased. The liquid ranges of 120-180 °C were observed for compounds with 5-6 carbon atoms in the alkyl chain. The low melting points and wide liquid ranges suggest potential applicability of these compounds for example as ionic liquids precursors.     

粉末冶金材料激光深熔焊接光致等离子体行为及控制

采用LSM2 4 0型全自动CO2 激光焊接机焊接粉末材料 ,研究不同粉末材料产生等离子体所需的临界激光功率。粉末配方为 :Fe粉 +15 %羟基Fe粉 ,Co粉 ,Ni粉 +15 %羟基Ni粉三种试样。研究结果表明 ,Fe ,Co ,Ni三种试样在CO2 激光作用下产生金属蒸气时的临界激光功率密度IC 为ICFe >ICCo >ICNi;等离子体得以有效控制的下限临界气流量QS 为QFeS 相似文献   

凝胶自燃烧法合成Bi0.5Na0.5TiO3纳米粉体

以Bi(NO3)3·5H2O、NaNO3和Ti(OC4H9)4为原料,采用凝胶自燃烧法合成了Bi0.5Na0.5TiO3纳米粉体,研究了粉体的晶相结构。结果表明:所合成的粉体粒子大小均匀,晶相单一,不需高温处理便能直接形成钙钛矿结构超细粉末。粉末经压片,1125℃烧结2h即可获得致密的烧结体,其d为98.1%。用SEM观察,烧结样品的平均粒径为2μm。     

硅微粉氧化性质研究

考察了硅微粉在空气、水、聚乙二醇(PEG)以及PEG水溶液几种介质中的氧化行为,并分析比较了两种不同切割过程所产生的硅微粉屑的氧化情况。结果显示:200℃下干燥空气中硅微粉不发生明显氧化;在高于80℃的水中放置10d,硅微粉发生明显氧化,形成非晶SiO2。与水及水溶液相比,PEG能在一定程度上阻止硅微粉的氧化。另外,带锯切割中产生的硅微粉屑氧化严重,而多线切割中产生的硅微粉切屑无明显氧化。     

酸洗前处理对叠层片式电感器焊接性的影响

采用电子扫描电镜和能谱分析研究了叠层片式电感器(MLCI)端电极的三层结构对焊接性的影响。利用氢氟酸(HF)具有强氧化性的特点对产品端电极银层进行微蚀前处理以起到整平作用,利于镀层的生长。试验结果证明前处理酸洗工艺能够有效改善产品镀层的焊接性。使用质量分数2%的HF进行酸洗,能够有效去除端电极银镀层上的玻璃相成分(SiO2),从而使电感器镀层表面上锡覆盖率大于90%。     

(Ca,Sr)(Zr,Ti)O_3系抗还原高频介质瓷料的研究

采用固相合成法制备了(Ca,Sr)(Zr,Ti)O3(简称CSZT)系电容器陶瓷材料,研究了主晶相组分对所制材料介电性能的影响。结果表明:通过调整主晶相CSZT中各组分的配比,再加入适量的烧结助剂,能得到一种可在还原气氛中烧结的高频介质瓷料,该瓷料可与镍内电极共烧,其相对介电常数约为89,介质损耗(tanδ)小于5×10–4,绝缘电阻达到1012Ω,介电常数温度系数为–1 037×10–6/℃。     

Shape‐Controlled Synthesis of Polyhedral Nanocrystals and Their Facet‐Dependent Properties

Growth of inorganic polyhedral nanocrystals with excellent morphology control presents significant synthetic challenges, especially when the development of synthetic schemes to make nanocrystals with systematic shape evolution is desired. Nanocrystals with fine size and shape control facilitate formation of their self‐assembled packing structures and offer opportunities for examination of their facet‐dependent physical and chemical properties. In this Feature Article, recent advances in the synthesis of nanocrystals with systematic shape evolution are highlighted. The reaction conditions used to achieve this morphology change offer insights into the growth mechanisms of nanocrystals. A novel class of polyhedral core–shell heterostructures fabricated using structurally well‐defined nanocrystal cores is also presented. Facet‐dependent photocatalytic activity, molecular adsorption, and catalytic and electrical properties of nanocrystals have been examined and are discussed. Nanomaterials with enhanced properties and functionality may be obtained through continuous efforts in the synthesis of nanocrystals with well‐defined structures and investigation of their plane‐selective properties.