二苯基二氯硅烷与双酚-A的缩聚反应动力学

研究了二苯基二氯硅烷与双酚-A在等克分子比条件下的缩聚反应动力学。采用熔融缩聚时反应速率规律性复杂,结果无法处理;而用萘、二苯醚、苯乙酮等溶剂稀释至一定程度后,前期反应动力学呈现二级反应规律。当温度相同时,溶剂极性越大,反应速率越快;在一定温度范围内反应速率常数的对数与绝对温度的倒数标绘呈线性关系,获得在萘、二苯醚、苯乙酮中缩聚反应的活化能分别为:17.1千卡/克分子,24.8千卡/克分子,10.3千卡/克分子。Lewis碱及其盐对此反应有显著的催化效应。验证了缩聚反应过程中体系极性改变时,反应速率即发生对应的变化,阐明了熔融缩聚反应速率不稳定的原因。提出了反应系按S_N2机理进行。     

Tuning the thermal conductivity of strontium titanate through annealing treatments

Strontium titanate(SrTiO_3) is a promising n-type material for thermoelectric applications. However, its relatively high thermal conductivity limits its performance in efficiently converting heat into electrical power through thermoelectric effect.This work shows that the thermal conductivity of SrTiO_3 can be effectively reduced by annealing treatments, through an integrated study of laser flash measurement, scanning electron microscopy, Fourier transform infrared spectroscopy, x-ray absorption fine structure, and first-principles calculations. A phonon scattering model is proposed to explain the reduction of thermal conductivity after annealing. This work suggests a promising means to characterize and optimize the material for thermoelectric applications.     

Influence of nitrogen and magnesium doping on the properties of ZnO films

Undoped ZnO and doped ZnO films were deposited on the MgO(111) substrates using oxygen plasma-assisted molecular beam expitaxy. The orientations of the grown ZnO thin film were investigated by in situ reflection high-energy electron diffraction and ex situ x-ray diffraction(XRD). The film roughness was measured by atomic force microscopy, which was correlated with the grain sizes determined by XRD. Synchrotron-based x-ray absorption spectroscopy was performed to study the doping effect on the electronic properties of the ZnO films, compared with density functional theory calculations.It is found that, nitrogen doping would hinder the growth of thin film, and generate the NOdefect, while magnesium doping promotes the quality of nitrogen-doped ZnO films, inhibiting(N_2)Oproduction and increasing nitrogen content.     

Ⅱ-Ⅵ比对分子束外延生长的ZnO/ZnMgO超晶格的相结构调控

在Zn_1-xMg_xO中,x=0.4~0.6仍为一个岩盐矿和纤锌矿共存的结构,影响了其晶格质量。本文利用等离子体辅助的分子束外延设备在c面蓝宝石衬底上外延生长了ZnO/ZnMgO超晶格,并改变其生长过程中的Ⅱ-Ⅵ比,利用原子力显微镜、X射线衍射、透射谱和X射线光电子能谱对样品进行了表征分析。发现在较低氧分压下制备的样品结构以岩盐矿为主导,而在较高氧分压下两相共存并以纤锌矿为主。这种相分离现象与裂解氧原子的密度有关。