Phosphaketenes as Building Blocks for the Synthesis of Triphospha Heterocycles

Unsaturated phosphorus compounds, such as phosphaalkenes and phosphaalkynes, show a versatile reactivity in cycloadditions. Although phosphaketenes (R?P?C?O) have been known for three decades, their chemistry has remained limited. Herein, we show that heteroatom‐substituted phosphaketenes, R₃E?P?C?O (E=Si, Sn), are building blocks for silyl‐ and stannyl‐substituted five‐membered heterocycles containing three phosphorous atoms. The structure of the heterocyclic anion depends on the nature of the tetrel atom involved. Although the silyl analogue [P₃C₂(OSiR₃)₂]^? is an aromatic 1,2,4‐triphospholide, the stannyl compound [P(CO)₂(PSnR₃)₂]^? is a 1,2,4‐triphosphacyclopenta‐3,5‐dionate with a delocalized OCPCO fragment. Because of their anionic character, these compounds can easily be used as building blocks, for example, in the preparation of a silyl‐functionalized hexaphosphaferrocene or the parent 1,2,4‐triphosphacyclopenta‐3,5‐dionate [P(CO)₂(PH)₂]^?. NMR spectroscopic investigations and computations have shown that the heterocycle‐formation reactions presented herein are remarkably complex.     

惰性盐辅助合成介孔石墨化碳片及其电容性能

以惰性盐KCl为模板、硝酸镍为金属催化剂镍源、葡萄糖为碳源,通过碳化处理制备了介孔石墨化碳片。利用扫描电子显微镜、透射电子显微镜、X-射线衍射仪和比表面测试仪对介孔石墨化碳片进行了表征。探讨了碳片形成的机理,采用三电极测试体系研究了介孔石墨化碳片电极材料的电化学性能。结果表明,10 g KCl制备的碳片比表面积最大(989 m2·g-1),在6 mol·L-1KOH电解液中,当电流密度为0.5 A·g-1时,比电容达到180 F·g-1;当电流密度达到10 A·g-1时,比电容维持在148 F·g-1,显示了电极具有较好的倍率性能;在10 A·g-1条件下,2 000次循环充放电测试后电容没有发生衰减,展示了在超级电容器方面的应用潜力。     

First Hyperpolarizability Evolutions of Some Extended Sesquifulvalene Compounds

Molecular orbital calculations of some extended sesquifulvalene compounds as O_n with olefins bridge and T_n with thiophenes bridge as well as their corresponding cyclopentadienyl‐iron(II) coordination compounds as IO_n and IT_n at the hybrid density functional theory level demonstrate that the dipole moment depends linearly on the molecular size (n), and the linear polarizability depends linearly on n² as well as the first hyperpolarizability also has a linear dependence on n³.     

A new target for synthesis of sandwiched beryllium, magnesium, and calcium dimers: C5H7-M-M-C5H7 and C4H4P-M-M-C4H4P

Group 2 bis-element sandwiches formed by homoleptic open sandwiches with formula C₅H₇-M-M-C₅H₇ and C₄H₄P-M-M-C₄H₄P (M = Be, Mg, and Ca) have been studied at the B3LYP/cc-PVDZ and BP86/6-311G(d,p) levels of theory. The predicted M-M bond distances are much shorter than in the equivalent isolated M-M dimer and indicate substantial Be-Be, Mg-Mg, and Ca-Ca bonding. An NBO analysis shows that each M-M unit contains a single covalent bond and that the unit is linked to the open pentadienyl and phospholyl ring via ionic bonds. We thus predict that these new compounds are viable synthetic targets.     

石墨双层在外力作用下的变形特性

利用原子力显微镜的探针将石墨的双原子厚片层进行撕裂操作,发现石墨片层只沿特定的方向撕裂和折叠;进一步还发现被撕开的片层在探针的作用力下有可能被压缩或拉伸,被压缩的片层会恢复到原来的形状,但被拉伸的片层却不能恢复到原来的形状.     

粘弹性几何非线性夹层梁动响应分析

本文选用考虑横向剪切效应的退化梁单元，引入几何非线性假设，对具粘弹性阻尼层的夹层梁动响应及其衰减效果进行了研究，得到了一些具有应用价值的结论。     

Resonance Vibrations and Dissipative Heating of Thin-Walled Laminated Elements Made of Physically Nonlinear Materials

The dynamic thermomechanical problem for thin-walled laminated elements is formulated based on the geometrically linear theory and Kirchhoff–Love hypotheses. A simplified model of vibrations and dissipative heating of structurally inhomogeneous inelastic bodies under harmonic loading is used. The mechanical properties of materials are described using strain-dependent complex moduli. A nonstationary vibration-heating problem is solved. The dissipative function, derived from the stationary solution, is used to specify internal heat sources. The amplitude–frequency characteristics and spatial distributions of the main field variables are studied for a sandwich beam subjected to forced vibrations     

宽板塑性弯曲成形过程中的板厚变化规律

根据宽板弯曲过程中的变形与应力分布特征，提出了一种计算弯曲过程中板料厚度随弯曲程度变化的新的近似解答方法．该方法基于塑性增量理论，应用塑性成形过程的体积不变假设和弯曲过程的平面假设．作为算例，得到了理想刚塑性材料的板料厚度、变薄系数以及应变中性层内移系数随板料弯曲内表面曲率半径变化的规律，并与实验数据进行了比较，两吻合良好．     

局部荷载作用下网架结构的拟夹层板分析法

把正交正放类网架结构简化为构造上正交异性的夹层板，采用考虑剪切变形的具有三个广义位移的平板弯曲理论来分析，给出了网架结构在局部荷载作用下的内力、位移解析计算公式，并用有限元方法进行了验证．     

板材冲压成形有限元数值模拟界面摩擦约束处理方法

基于弹塑性大变形板材冲压成形增量有限元法,采用线性弹簧单元提出一种空间三维板材冲压成形等效界面摩擦力的处理方法.这种方法的优点是可以反映界面摩擦力的同步、被动产生效果,同时它还可以保证约束后刚度矩阵的对称性.将提出的摩擦约束处理算法引入自主开发的板材成形模拟软件FASTAMP,计算了汽车油底壳的成形过程,计算结果的厚度分布与实际冲压件吻合比较好,验证了等效界面摩擦力约束处理方法的有效性.