Pom-Pom分子在平面收缩流场中的流变行为

用基于管子理论发展的XPP(extended Pom-Pom)模型描述支化高分子熔体——低密度聚乙烯(LDPE)的分子流变特性,实现了从分子微观结构到宏观响应的跨尺度模拟.引入有限增量微积分(FIC)过程重构了压力稳定质量守恒方程以克服因流体不可压缩性引发的压力场空间分布虚假振荡现象.采用离散的弹性——黏性应力分裂技术(DEVSS)以在缺失纯黏性项情况下保持动量方程弱形式中的椭圆项贡献.利用迎风流线(SU)方法离散黏弹性XPP本构方程中的对流项,以基于Crank-Nicolson隐式差分格式的迭代稳定分步算法求解质量、动量守恒方程和本构方程.采用等低阶有限元模拟了平面黏弹性收缩流,考察了不同Weissenberg数、支化程度和分子结构参数对Pom-Pom分子在收缩流场中流变行为的影响,数值结果与相关文献和试验结果吻合得较好.     

α-和β-三氟萘乙烯的热二聚 阻旋异构体的生成

α-和β-三氟萘乙烯在120℃下热二聚,产物用HPLC分离。对β-三氟萘乙烯,可分离到三个纯的二聚体。而对α-三氟萘乙烯,虽然分离到的热二聚产物也是三个组分,但其中一个仍然是混合物。由~(19)F,~1HNMR,MS分析表明是环化二聚产物,即1,2-二萘六氟环丁烷的反式及顺式阻旋异构体。     

MICROENVIRONMENTAL EFFECTS OF THE HELICAL CONFORMATIONS OF AMYLOSE AND ITS DERIVATIVES——CATALYTIC EFFECTS OF SODIUM CARBOXYMETHYLAMYLOSE ON THE HYDROLYSIS OF VARIOUS ESTERS OF N-ALKYL-3-HYDROXYPYRIDINIUM IODIDE

Hydrolysis of various carboxylic esters of N-alkyl-3-hydroxypyridinium iodide(2—5) has been studied, both in the absence and in the presence of sodium carboxymethylamylose(NaCMA 1). In the absence of Na-CMA, the hydrolysis of all four substrates follows 2nd-order kinetics when HPO_4~- and CH_3CO_2~- ions are used as the attacking nucleophites. In the presence of 1, however, the course of the reaction depends on the structure of the substrates. For 2 and 3, the observed rate constants k_(obs) are independent of the eoncentration of 1 added, but for those with long hydrocarbon chains, i. e. 4 and 5, the hydrolysis follows MichaelisMenten kinetics. All other experimental results also indicate the formation of supramolecular(incluston) complexes between the Na-CMA host molecules in helical conformations and theesters 4 and 5. In comparison with the bimolecular processes in the bulk phase, the catalytic efficiencies(k_c/K_d) of these supramolecular systems are 3.7×10~4 and 1.7×10~4 times that of the aceta     

柔性烃链定位光氯化反应的初步研究

对于刚性分子的远距离定位光卤化反应已有成功的报导,柔性链分子由于不易找到合适的环境或基架来控制链的定向,因此定位反应遇到很大困难。本工作则试图利用处于反向胶团中疏水分子的相对有序排列的特性来对柔性链分子定位的光氯化反应作试探性研究。合成了不同长度的对-碘代苯基羧酸I-C_6H_4-(CH_2)_nCOOH(1)并与反应受物正十二醇生成相应的酯,经与氯气反应生成二氯碘代苯基羧酸十二酯Cl_2I-C_6H_4-(CH_2)_nCOOC_(12)H_(25)(2),将(2)     

基于极大似然估计的BP算法及其在深基坑开挖参数辨识中的应用

本文采用人工神经网络BP算法对深基坑开挖工程中的参数进行辨识,将某些现场实测值作为网络输入,土层物性参数作为网络的输出, 限元计算取得学习样本来训练网络,从而地深基坑开挖工程中的参数进行辨识的目的,同时,本文提出了将极大似然估计引入BP学习算法中,可以考虑学习样本和网络输入（现场产测值）的误差,可以求得所辨识参数的可靠度,本文还对动态调整BP学习算法的学习速度因子,冲量系数以加快网络学习速度的算法进行了研究,本文算例表明本文算法训练速率可比传统BP算法快10倍以上。     

高温闪烁晶体Ce∶YAP的生长研究

Ce∶YAP晶体具有优良的闪烁性能,其主要特点是光产额大,衰减时间短,发射峰与光电倍增管的接收范围相匹配,在γ射线探测、核医学等方面有着广阔的应用前景.我们用提拉法生长了不同掺杂浓度的Ce∶YAP晶体,成功地解决了在生长过程中出现的晶体开裂及孪晶问题,并对晶体生长过程中的爬料、纯YAP晶体着色等现象作了讨论.X射线激发发射谱表明晶体的发射峰在388nm,吸收测试则显示晶体在254nm、366nm处有两个吸收峰.     

YAP晶体变色现象的研究

YAlO3(YAP)晶体具有优良的物理和化学性能,在许多方面都有广泛的应用前景.我们在对闪烁晶体Ce∶YAP的研究过程中,发现了YAP晶体的变色现象.本文利用晶体透过谱对其颜色的变化进行了研究.不同的退火气氛及不同的掺杂成份对晶体颜色有较大影响,H2气氛退火或掺杂Ce元素使晶体颜色变浅,而在空气中退火或掺杂Yb元素则使晶体颜色加深.针对这一变色现象,我们认为是在晶体生长过程由于电荷补偿的需要而产生的O-心的吸收作用导致的.不同的O-心浓度其吸收作用不同,从而使晶体在400nm附近的透过率发生变化.采用这一模型可以对晶体颜色的变化及不同退火条件和掺杂元素的影响作出合理的解释.     

Electron-transfer fluorescence quenching processes in coaggregates between excited N-alkylcarbazoles as electron donors and 2, 4-dinitrophenyl carboxylates or pentafluorophenyl carboxylates as acceptors

Electron-transfer processes facilitated by hydrophobic-lipophilic interaction ( HLI) between excited N-alkylcar-bazoles (1-n, n=4, 8, 12, 16) as electron donors and 2,4-dintrophenyl carboxylates (2-n, n = 4, 8, 12, 16) or pentafluorophenyl carboxylates (3-n, n = 4, 8, 12, 16) as electron acceptors have been investigated by means of fluorescence spectroscopy in aqueous or aquiorgano binary mixtures. The fluorescence quenching of -n * by 2-n or -n indicates that preassociation precedes the electron transfer. The extent of HLI-driven coaggregation of the acceptor and the donor may be assessed from the B value of the equation I0/I = A B [Q]. The chain-length effect and possibly also a chain-fold-ability effect, as well as the solvent aggregating power (SAgP) effect have been observed. Comparison of the quenching constants (B) for 1-n * /2-n combinations and 1-n * / 3-n combinations shows that the order of increasing R values for the quenching processes is 3-n < 2-n.     

Aggregating tendencies of some N-alkylcarbazoles

Aggregation of some nitrogen-containing heterocyclic compounds have been investigated by means of fluorescence spec-troscopy in aqueous or aquiorgano binary mixtures of different Φ values for the first time. The aggregators studied are N-butylcarbazole (CBZ-4), N-octylcarbazole (CBZ-8), N-do-decylcarbazole (CBZ-12), and N-hexadecylcarbazole (CBZ-16). Their aggregating tendencies have been evaluated by measuring their critical aggregate concentration values (CAgC's). Our results indicate that the N-alkylcarbazoles, just like the anthracene derivatives with different chain-lengths, can also be used as fluorescence probes for evaluating aggregating tendencies or CAgC values.     

结构分析有限元程序JIGFEX和它的新发展

本文简要介绍了结构静、动力有限元分析程序ＪＩＧＦＥＸ的主要特色和它在土与结构相互作用、饱和土分析、动态子结构分析、非线性接触分析、高层建筑抗震分析、温度场与热传导分析、群论结构分析以及平稳与非平稳多点随机地震激励响应分析等多方面最新发展．