掺锗提高VO2薄膜的相变温度机理研究

二氧化钒(VO₂)作为一种长久以来备受关注的新型可逆相变材料,发展潜力巨大,其相变温度(T_MIT)的调控一直是研究热点。本文主要利用锗离子作为掺杂离子探索其对VO₂薄膜T_MIT的影响,并尝试解释其内部作用机理。在约1 cm²大小抛光的氧化铝薄片上沉积了一系列含不同比例锗离子VO₂薄膜。研究发现锗离子作为掺杂离子确实有利于T_MIT的提高(本课题T_MIT最大可达84.7 ℃)。T_MIT提高的主要原因是锗离子的引入能够强化单斜态V-V二聚体的稳定性,进而增强单斜态的稳定性,使得低温单斜态向四方金红石态转变更加困难。     

Ni单原子催化剂表面CO2电还原动力学的电化学谱学解析

针对Ni单原子催化剂表面的CO₂电还原反应(CO₂RR), 提出了以Ni为活性位点的“单中心”机理以及同时借助Ni位点还原和碳氮锚定位水解的“双功能”机理. 依据稳态极化的实验结果, 开展了CO₂RR的动力学解析与模型参数的敏感性分析; 借助暂态模型方程, 分别获取可表达CO₂RR线性与非线性频响特征的电化学阻抗谱(EIS)与总谐波失真(THD)谱. 研究结果表明, CO₂的溶解分压对CO₂RR活性影响最显著. 若CO₂RR遵循“单中心”机理, Ni位点COOH_ads的形成为速率控制步骤; 但若为“双功能”机理, 碳氮锚定位的水解与Ni位点的CO_2,ads还原同为速率控制步骤. EIS理论上可用于区分CO₂RR的“单中心”机理与“双功能”机理; 与之相比, THD谱在CO₂RR的机理识别中并无优势.     

晶格畸变检测仪研究碳化硅晶片中位错缺陷分布

利用晶格畸变检测仪研究了SiC晶片位错分布情况,通过对熔融KOH腐蚀后的SiC晶片进行全片或局部扫描,从而得到完整SiC晶片或局部区域的位错分布。与LEXT OLS4000 3D激光共聚焦显微镜扫描腐蚀图进行比较,晶格畸变检测仪扫描腐蚀图可以将晶片上位错腐蚀坑信息完全呈现出来,且根据腐蚀坑呈现的颜色及尺寸大小,可以分辨出三种不同类型的穿透型位错,其中黑点腐蚀坑对应螺位错,小尺寸白点腐蚀坑对应刃位错,大尺寸白点腐蚀坑对应混合型位错。采用晶格畸变测试仪研究了4英寸(101.6 mm)N型4H-SiC晶体不同生长时期的位错密度及分布情况,结果表明随着晶体生长,位错密度呈现逐渐降低的趋势,生长后期晶片的总位错密度降为生长前期晶片总位错密度的近1/3,有利于反馈位错缺陷在SiC晶体生长过程中的延伸和转化特性信息,以指导SiC晶体生长工艺改进。     

An investigation of the electron density of a Jahn–Teller‐distorted CrII cation: the crystal structure and charge density of hexakis(acetonitrile‐κN)chromium(II) bis(tetraphenylborate) acetonitrile disolvate

In the crystal structure of the title homoleptic Cr^II complex, [Cr(CH₃CN)₆](C₂₄H₂₀B)₂·CH₃CN, the [Cr(CH₃CN)₆]²⁺ cation is a high‐spin d⁴ complex with strong static, rather than dynamic, Jahn–Teller distortion. The electron density of the cation was determined by single‐crystal X‐ray refinements using aspherical structure factors from wavefunction calculations. The detailed picture of the electronic density allowed us to assess the extent and directionality of the Jahn–Teller distortion of the Cr^II cation away from idealized octahedral symmetry. The topological analysis of the aspherical d‐electron density about the Cr^II cation showed that there are significant valence charge concentrations along the axial Cr—N axes. Likewise, there were significant valence charge depletions about the Cr^II cation along the equatorial Cr—N bonds. These charge concentrations are in accordance with a Jahn–Teller‐distorted six‐coordinate complex.     

Bloch Constant on α-Bloch Mappings of the Unit Ball

This note is denoted to establishing sharp distortion theorems for subclasses of α-Bloch mappings defined in the unit ball of Cn with critical points.Furthermore,the estimates of Bloch constant with respect to these subclasses are given.     

Geometric analysis of anharmonic downward distortion following paths

A mathematical aspect of the anharmonic downward distortion following (ADDF) path is discussed. The ADDF method is utilized as an automated reaction path search method, which can explore transition state geometries on a potential energy surface from a potential minimum. We show that the maximum number of the ADD stationary paths intersecting the potential minimum is 2^{f + 1} ? 2 , where f denotes the degree of freedom of the system. We also show that the bifurcation of the ADD stationary path is essential to detect all the transition states connected from a given minimum. The ADDF computation is demonstrated for a H₂O molecule in which pitchfork bifurcation is observed.     

Analysis of Non-innocence of Phosphaquinodimethane Ligands when Charge and Aromaticity Come into Play

Several phosphaquinodimethanes and their M(CO)₅ complexes (M=Cr, Mo, W) and model derivatives have been theoretically investigated regarding the quest of non-innocence. Computed structural and electronic properties of the P-Me/NH₂ substituted phosphaquinodimethanes and tungsten complexes revealed an interesting non-innocent ligand behaviour for the radical anion complexes with distonic ion character and a strong rearomatization of the middle phenyl ring. The latter was further probed taking also geometric aromaticity (HOMA) and quinoid distortion parameters (HOMQc) into account, as well as NICS(1). Furthermore, the effect of the P-substitution was investigated for real (or plausible) complexes and their free ligands focusing on the resulting aromaticity at the middle phenyl ring and vertical one-electron redox processes. The best picture of ligand engagement in redox changes was provided by representing NICS(1) values versus HOMA and the new geometric distortion parameter HOMQc8.     

Improving the impact property and heat‐resistance of PLA/PC blends through coupling molecular chains at the interface

The influences of both the molecular structure and the melt viscosity differences between Poly(lactic acid) (PLA) and polycarbonate (PC) on the interpenetration of molecular chains at the interface were investigated by comparing the dynamic mechanical properties and morphologies of the as‐prepared PLA/PC solution‐casting blends with those of their corresponding annealed (180°C, 8 h) samples or PLA/PC melt blends. Additionally, two chain extenders containing epoxy groups (ADR and TGDDM) were used to improve the interfacial strength. Subsequently, the interpenetration of PLA and PC molecular chains at the interface was also surveyed. Finally, the effects of the morphology formed by after adding ADR or TGDDM on the impact property, and heat resistance were discussed. The results showed that there was no interpenetration of molecular chains at the interface in PLA/PC melt blends because of the serious hindrance of the molecular structure and the melt viscosity differences. Although the interfacial strength achieved significant increase after adding ADR or TGDDM, the increase of the interfacial strength should be caused by the connection of ADR or TGDDM molecules with PLA and PC molecules at the interface through chemical bonds rather than the entanglements of PLA and PC molecular chains because of no interpenetration of PLA and PC molecular chains at the interface. Thus, the morphology formed after adding ADR or TGDDM is still the type of complete phase separation, which may be the most suitable morphology for achieving high impact and heat resistance PLA/PC blends because these two properties strongly depend on the crystallinity of PLA phase. Copyright © 2015 John Wiley & Sons, Ltd.     

基于运动约束解过约束并联机构变形协调方程

提出利用运动约束关系来间接求解过约束并联机构变形协调方程．首先介绍了该方法的原理，接着分别针对平面和空间过约束并联机构，详述该方法的解决步骤，结果验证了该方法的正确性，从中还可看出该方法在求解复杂过约束并联机构时非常简洁，最后介绍了采用该方法解决多度过约束问题．     

A PREDICTIVE APPROACH TO THE IN-PLANE MECHANICAL PROPERTIES OF STITCHED COMPOSITE LAMINATES

This contribution attempts to model the alteration of the in-plane elastic properties in laminates caused by stitching,and to predict the in-plane effective tensile strength of the stitched composite laminates.The distortion of in-plane fibers is considered to be the main cause that affects the in-plane mechanical properties.A fiber distortion model is proposed to characterize the fiber misalignment and the fiber content concentration due to stitching.The undistorted region,the fiber distortion region,the resin-rich pocket and the through-thickness reinforcement section are taken into account.The fiber misalignment and inhomogeneous fiber content due to stitching have been formulated by introducing two parameters,the distortion width and maximum misalignment.It has been found that the ply stress concentration in stitched laminates is influenced by the two concurrent factors,the stitch hole and inhomogeneous fiber content.The stitch hole brings about the stress concentration whereas the higher fiber content at the local region induced by stitching restrains the local deformation of the composite.The model is used to predict the tensile strength of the [0/45/0/-45/90/45/0/-45]_(2s) T300/QY9512 composite laminate stitched by Kevlar 29 yarn with different stitching configurations,showing an acceptable agreement with experimental data.