颗粒柱塌落中的尺寸效应和瞬态流变性研究

颗粒材料是自然界和工程中广泛存在和普遍应用的材料,泥石流、滑坡和混凝土等均可视为颗粒材料。颗粒材料研究有助于更好地控制相关自然灾害或利用其某些特性。对颗粒材料柱体的塌落动力学研究不仅可以方便理解颗粒材料在瞬态流动时的流变性,还可以引申到泥石流等岩土材料的运动与堆积形态。本文利用扩展多面体离散单元法对颗粒堆积柱的塌落进行了细致的研究,探索高宽比、摩擦系数以及颗粒柱相对尺寸等对柱体塌落的影响。对颗粒集合进行分网并分析每个网格内的应力与应变率之间的关系,讨论其瞬态本构关系。相关研究对于深入理解颗粒材料重力流的动力学性质以及颗粒集合体的堆积形态具有重要意义。     

Facile Synthesis of S-Fused Multi-Membered Polycyclic Heterocycles: A Construction Strategy towards Thermally Stable Thiepine Derivatives

S-fused heterocycles have become popular building blocks to construct functional polycyclic compounds. In contrast to the abundant synthetic methodologies for thiophene-fused aromatics, the synthesis of S-heterocycles containing six-membered thiopyran and seven-membered thiepine rings is much less reported owing to their unfavorable synthetic protocols and the thermal instabilities. Herein, a series of thiepine-containing polycyclic S-heterocycles have been successfully synthesized via different synthetic routes which involve initial construction of sulfur bridges and final ring-closure reactions. Therefore, the dilithium intermediates are excluded, which facilitates the fusion on the thiepine ring with different S-heterocycles, including thiophene and thiopyran derivatives. Typically, a S-fused multi-membered polycyclic compound simultaneously involving thiophen, thiopyran, and thiepine rings has been successfully prepared. Interestingly, nucleus-independent chemical shift calculations reveal that the incorporated thiopyran and thiepine rings demonstrate aromatic and nonaromatic characteristics, respectively. Moreover, the thermal stabilities of the thiepine derivatives have been tremendously improved after the fusion on the three vinyl groups in the thiepine unit, which is attributed to the enhancements of the activation energies for the S-extrusion reactions, as revealed by density functional theory calculations. Therefore, our findings not only provide a facile synthetic methodology for S-fused multi-membered polycyclic heterocycles, but also furnish a novel construction strategy towards thermally stable thiepine derivatives.      

LaF3纳米线的低温溶剂热法制备及形成机理

LaF₃ nanowires with high aspect ratios have been prepared via a low-temperature solvothermal method using LaCl₃ and KF or NH₄F as starting materials in absolute alcohol at 160 ℃ for 12 h. XRD pattern and TEM images show that the products are hexagonal structure with diameter of 80 nm and length up to 8 μm. The lanthanum sources played most important roles, reaction temperature and time also played important roles in the morphology control of final LaF₃ products. The optimal conditions for ideal LaF₃ nanowire are at a reaction temperature of 160 ℃ and reaction time for 14 h using LaCl₃ and NH₄F as starting materials. A possible formation mechanism for LaF₃ nanowires is proposed.