Mild and efficient Cs2CO3-promoted synthesis of phosphonates

A mild and convenient synthesis for phosphonates using cesium carbonate (Cs₂CO₃), tetrabutylammonium iodide (TBAI) and DMF was developed at room temperature. Numerous dialkyl phosphites were screened using a diverse array of alkyl halides and these reaction conditions were found to be highly efficient producing various phosphonates exclusively in moderate to high yields.     

Determination of trace metals in industrial boron carbide by solid sampling optical emission spectrometry. Optimization of DC arc excitation (current, atmosphere and chemical modifier)

Graphite arc emission spectrometry has become possible as a result of the invention of novel types of optical spectrometers with Echelle-optics and semiconductor array detectors, and by the application of electronically controlled, high current arc generators. An optimization of the excitation parameters to boron carbide analysis is reported here, measuring background corrected line intensities that were integrated for the time of total evaporation of 5 mg boron carbide sample with or without added chemical modifiers. The following set of experimental conditions were compared with respect of analytical sensitivity and precision: (A) no modifier, Ar + O₂ (20%), 16 A; (B) sample + graphite powder (1 + 1), Ar + O₂ (20%), 16 A; (C) sample + CaF₂ (1 + 1), Ar, 25 A; (D) sample + CaF₂ + graphite powder (1 + 1 + 1), Ar, 25 A. The graphite powder modifier resulted in improved precision in general, and the CaF₂ was effective as a plasma ionization buffer and fluorinating agent. The best compromise was found under conditions B, when oxygen was present in the discharge atmosphere. This is likely due to the stepwise conversion of the boron carbide matrix to the more volatile boron oxide. Under conditions B, detection limits in the ranges of 0.3–9 μg g⁻¹ for Al, Ca, Cr, Cu, Fe, Mg, Mn and Si and that of 18–38 μg g⁻¹ for Ti, W, and Zr were attained. Average RSDs of 10.2 and 9.7% were found, respectively, without and with internal referencing to boron.     

A Sensitive Spectrophotometric Determination of Nitrite in Water and Soil

A highly sensitive spectrophotometric method for the determination of nitrite in water and soil has been developed. The reaction of nitrite with acidified potassium iodide to liberate iodine which oxidizes leuco‐crystal violet (LCV) to form crystal violet having absorption maxima at 590 nm forms the bases of this method. In aqueous medium the system obeys Beer's law in the range of 0.1 to 1.0 μg per 25 mL (0.004–0.04 ppm), while in an extractive system the range is 0.025–0.25 μg in 100 mL (0.00025–0.0025 ppm). The molar absorptivity and Sandell's sensitivity were found to be 1.54 × 10⁶ 1 mol^?1 cm^?1 and 44 pg cm^?2, respectively.     

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.     

甲烷浓度对碳化硅基底金刚石薄膜摩擦性能影响

利用热丝化学气相沉积法(HFCVD)在碳化硅基底上制备金刚石薄膜,采用场发射扫描电子显微镜、拉曼光谱仪、原子力显微镜研究了在不同甲烷浓度条件下制备的金刚石薄膜表面形貌及物相组成,在干摩擦条件下通过往复式摩擦磨损实验测试并计算了已制备金刚石薄膜的摩擦系数和磨损率,结合物相分析及摩擦磨损实验结果分析了甲烷浓度的改变对金刚石薄膜摩擦磨损性能的影响。结果表明,由于甲烷气体含量的升高,金刚石薄膜结晶质量下降,薄膜由微米晶向纳米晶转变。摩擦磨损实验结果显示:3%甲烷浓度条件下制备的金刚石薄膜耐磨性较好,磨损率为2.2×10^-7 mm³/mN;5%甲烷浓度条件下制备的金刚石薄膜摩擦系数最低(0.032),磨损率为5.7×10^-7 mm³/mN,制备的金刚石薄膜的耐磨损性能相比于碳化硅基底(磨损率为9.89×10^-5 mm³/mN)提升了两个数量级,显著提高了碳化硅基底的耐磨性。     

Carbon Nanotube Supported Molybdenum Carbide as Robust Electrocatalyst for Efficient Hydrogen Evolution Reaction

Molybdenum carbide is considered to be one of the most competitive catalysts for hydrogen evolution reaction (HER) regarding its high catalytic activity and superior corrosion resistance. But the low electrical conductivity and poor interfacial contact with the current collector greatly inhibit its practical application capability. Herein, carbon nanotube (CNT) supported molybdenum carbide was assembled via electrostatic adsorption combined with complex bonding. The N-doped molybdenum carbide nanocrystals were uniformly anchored on the surfaces of amino CNTs, which depressed the agglomeration of nanoparticles while strengthening the migration of electrons. The optimized catalyst (250-800-2h) showed exceptional electrocatalytic performance towards HER under both acidic and alkaline conditions. Especially in 0.5 M H₂SO₄ solution, the 250-800-2h catalyst exhibited a low overpotential of 136 mV at a current density of 10 mA/cm² (η₁₀) with the Tafel slope of 49.9 mV dec⁻¹, and the overpotential only increased 8 mV after 20,000 cycles of stability test. The active corrosive experiment revealed that more exposure to high-activity γ-Mo₂N promoted the specific mass activity of Mo, thus, maintaining the catalytic durability of the catalyst.     

激光微织构硬质合金表面润湿性

为了研究硬质合金表面激光微织构对其表面润湿性的影响,利用光纤激光不同功率（3,5,7,9,10 W）及不同加工次数（1,2,3,4,5）加工微凹坑,采用VHX1000c超景深三维显微镜、光学显微镜分析微凹坑形貌,利用CAM 200光学接触角仪测量表面微织构（微凹坑直径、深度和织构密度）与润湿性之间的关系。结果表明：随着激光功率的增大,微凹坑深度增加,直径变化不明显;硬质合金表面的亲水性能随着微凹坑深度的增加而减小;随着微凹坑直径的增大,亲水性增强;随着微织构密度的增加,亲水性出现极值。     

包覆板材料为陶瓷时平板装药的防护性能

运用口径36mm的精密成型装药实验,研究了等效厚度相同的碳化硅和氧化铝陶瓷平板装药的防护性能,并与包覆材料为钢的平板装药进行了对比。运用LS-DYNA3D软件,对平板装药与聚能装药的作用过程进行了三维数值模拟。实验结果显示,对于此结构的平板装药,碳化硅和氧化铝陶瓷平板装药使聚能装药侵彻能力分别下降了88%和82%,优于钢板的防护性能。数值模拟结果显示,陶瓷包覆板从边缘至中心依次出现断裂和粉碎现象,钢板与射流后部作用为断续干扰,而陶瓷板为连续干扰。

     

SiC表面电磁模态及其非线性优化

基于特殊的SiC周期性结构,理论分析了SiC表面特殊电磁模态的激发特性,并利用数值模拟的方法研究了该周期性结构的红外辐射/吸收特性。模拟结果表明该周期性结构在电磁波照射下可以支持多种电磁模态的激发,并且多种电磁模态之间存在相互耦合现象,证实了理论分析的结果。基于非线性优化算法,分别对结构在单个频率整个角度范围内的红外辐射/吸收特性,以及整个研究频段内的垂直方向红外辐射/吸收特性进行了优化。优化的结果显示,相比于原来的结构,优化后结构的等效发射率/吸收率有较显著地提升。     

乙醇-环己烷体系中NaI活度系数的测定与计算

由于非水溶剂的应用日趋广泛,促使物理化学工作者对于溶剂和溶液性质进行研究,同时开展了有关物理化学数据的测定和积累工作,以利于指导实践[1]。目前文献报道含水混合溶剂中的电解质活度系数较多,但非水混合溶剂中电解质活度系数报道较少。电解质浓溶液活度系数的计算方法目前应用较广的是Pitzer半经验算法[2]。Pitzer的算法中具体物系的β(0)、β(1)等系数需从实测活度系数数据拟合求得。孙仁义等通过测定汽液平衡盐效应的方法研究了盐在混合溶剂中的活度系数[3-4]。最近孙仁义等[5]提出了双液比固定条件下含盐体系汽液平衡数据热力学一…