中相微乳液的介电弛豫谱解析及弛豫机制研究

对由SDS、CTAB、正庚烷、正丁醇和盐水组成的中相微乳体系进行了介电测量,在不同盐度下低频段出现显著的介弛豫现象,它给出了弛豫时间随盐度的变化关系。通过解析介电谱获得了体系内部结构和电性质等信息,几个介电模型和理论公式被用来解释解析的结果。对弛豫时间的计算结果发现,该弛豫是由多种极化机制参与、界面极化为支配的动力学过程。介电解析和模型计算相互验证,结果暗示着体系盐度变化对中相微乳结构变化的影响和可能的转化机制。     

较快一级化学反应的热动力学研究法: 热弛豫法

分析了非稳态传热情况下热导式热量计的动态性能,通过对输出信号的剖析,建立了热导式热量计冷却常数的经验动态模型。通过对热弛豫现象的分析,建立了可用于研究快速化学反应的热动力学研究法-热弛豫法,应用此种量热研究法可用于研究速率常数小于5s^-^1的一级化学反应。研究了25℃下乙酸甲酯、甲酸乙酯和甲酸甲酯在水溶液中的皂化反应,其计算结果与文献值相吻合,从而验证了热弛豫法的正确性。     

Creation of Unstable Particles and Decoherence in Semiclassical Cosmology

We consider a simple cosmological model in orderto show the importance of unstable particle creation forthe validity of the semiclassical approximation. Usingthe mathematical structure of rigged Hilbert spaces we show that particle creation is theseed of decoherence which enables the quantum toclassical transition.     

LaOX-Pr^3^+(X=Cl, Br)体系的荧光特性及其配位场理论解析

LaOX-Pr^3^+(X=Cl,Br)体系在室温和液氮温度下均只观察到^3P~0能级的发射,其原因在于Pr^3^+离子的4f5d激发态具有较高能量(>37kK),且^3P~2,^3P~1向^3P~0存在有效的电子驰豫;本文基于DSCPCF配位场模型的计算结果,对该体系的发射光谱和激发光谱进行了理论归属,实测峰位与计算值较好吻合。     

Nafion修饰电极还原计时电位溶出法的理论和验证

本文推导了Nafion修饰电极还原计时电位溶出法的过渡时间和电位-时间曲线方程式。经过验证,实验结果与理论相符。     

二元混合溶剂的NMR弛豫研究

本文测定了纯CH3OD, DMSO-d6中^2D和DMF中^1^4N的弛豫时间. 参照文献所列核四极矩偶合常数, 按公式计算它们的液体分子取向相关时间, 参照Hertz等的假设, 认为在混合溶剂中各组分的核四极矩偶合常数基本不变, 与纯质相同, 并计算了各组分分子在各个混合溶剂中的取向相关时间, 从而初步讨论了混合溶剂中各组分分子间的相互作用.     

一种新的稀土配合物结构分析方法-无顺磁位移混合三稀土法

提出无顺磁位移混合三稀土配合物结构分析方法, 并以丙氨酸稀土为例, 选取Eu-Yb-Pr和Er-Yb-Pr体系从实验上予以验证。研究发现, 通过选择适当的三种顺磁性稀土离子以一定比例混合, 可以抵消顺磁诱导位移, 仅保留顺磁弛豫增强效应, 因而可直观地从谱线半高宽(W1/2)看出稀土配合位点, 从纵向弛豫时间(T1)或谱线半高宽计算稀土与配体磁核间的相对距离。     

STUDY ON INTERMITTENT SHEAR FLOW AND RELAXATION BEHAVIOR OF THERMOTROPIC LIQUID CRYSTALLINE POLYMER

Intermittent shear flow including start-up flow and small oscillatory amplitude time sweep or stress relaxation after cessation of shear flow was used to study the rheological behavior and internal structure of thermotropic liquid crystalline polymer (TLCP). There are two kinds of intermittent shear flow: all start-up flows are in the same direction (intermittent flow forward: IFF) and start-up flows change their directions alternately (intermittent flow reversal: IFR). The results show that the stress of start-up flow of IFF and IFR in the test process is not superposed, indicating different changes of internal structure of thermotropic LCP (TLCP). Two main factors affect structure changes in the experimental time scale. One relates to long-term texture relaxation process, the other is an interchain reaction that becomes important after 30 min. The two factors raise the stress of IFF, but express complex effects for the stress of IFR. The latter factor becomes very important at long time annealing process. The relaxation behavior was also studied by the application of wide range relaxation spectrum calculated from the combined dynamic modulus, which gave three characteristic relaxation times (0.3, 10 and 600 s) ascribable to the relaxations of less-phase orientation, domain orientation, and domain deformation, respectively. The result also shows that the domain coalescence (texture relaxation), a long relaxation time, is a much slow process and lasts beyond 2400 s of the test time.     

钪的直链聚醚配合物及其NMR波谱研究

本文首次获得钪的直链聚醚配合物, 发现共存阴离子不同对配合物组成与性质有显著影响。在高氯酸钪体系中得到双核及高电解质类型的配合物, 利用测定^1^3C NMR自旋-晶格弛豫时间T1等方法, 证明所合成的配合物中钪与直链聚醚的配位氧原子直接结合及超过常见配位数为6的有意义结果。     

用^2^9SiNMR谱鉴定手性烷氧基氯硅烷与对映体醇类反应产物的纯度和构型

手性烷氧基氯硅烷与对映体醇反应生成非对映体, 可用^2^9SiNMR谱测定醇类对映体纯度, 相对误差在±5%以内, 非对映体SS的^2^9Si化学位移通常比相应的SR异构体出现在较高场。