稀土与含硫有机配体配合物的研究: I. 二乙氨基荒酸稀土配合 物Et~2NH~2 [RE9S~2CNEt~2)~4]的合成、表征与结构

在干燥氮气氛中,以乙醇为溶剂制备出稀土与二乙氨基荒酸二乙铵形成的十五个配合物,测定了它们的红外及紫外光谱、热谱和电导,确定该类配合物组成为Et~2NH~2[RE9S~2CNEt~2)~4](RE=La-Lu,Y;Pm除外)。镧配合物的X射线结构分析表明,在该配合物中四个二乙氨基荒酸根各通过两个硫原子与镧离子成键,从而形成八配位的十二面体阴离子,并与二乙铵阳离子形成离子缔合型的配合物分子。     

液相沉积法制备光催化活性TiO2薄膜和纳米粉体

采用液相沉积法，在35℃通过向六氟钛酸铵水溶液中添加硼酸和结晶诱导剂锐 铁矿型TiO2纳米晶，沉积出具有光催化活性的Ti02薄膜和纳米粉体．用XRD，AFM， 阶梯仪,UV-vis，BET法对Ti02薄膜和粉体的沉积条件、结构、厚度和性能进行了测 定和表征，并用亚甲兰的降解，评价了TiO2薄膜和纳米粉体的光催化活性．结果表 明，当反应物六氟钛酸铵与硼酸的摩尔比为1：2—1：4时，沉积的粉体和薄膜含有 锐钛矿相Ti02；经300℃热处理的Ti02薄膜和纳米粉体具有最高的光催化活性，它 的光催化活性是未经热处理前的5倍．本文还解释了经300℃热处理的薄膜和纳米粉 体具有最高光催化活性的原因．     

Nanoindentation Experimental Approach and Numerical Simulation of Al/Cr Bilayer Films

The Al/Cr double-layer film structure samples (thickness, 1200 nm) were prepared by the magnetron sputtering method. To investigate the mechanical properties, the samples were measured by using a nanoindentation instrument. The test results showed the nonlinearity and different modes of the main mechanical properties by comparing the macro-scale structure samples with other samples of similar materials. Based on the test, the elastic modulus and hardness of thin film structures can be calculated by considering different loads to conduct multi-point indentations. Meanwhile, the relationships between the mechanical parameters can be investigated based on these Al/Cr double-layer film structure samples. To validate the test, numerical analysis was developed using a finite element method to simulate the loading and unloading process of indentation. The simulation results were compared with the results of experiments to illustrate the validity of both the test and simulation to a certain extent. The investigation builds not only an experimental basis for practical applications for future study, but also supplies a complementary means of verification for theoretical analysis.     

Sliding Wear Studies on Aluminium–Copper Composites

Metal–metal composites are prepared by dispersing copper particulates in an aluminium matrix using stir-cast technique. Behaviour of the same is compared with the alloy having similar composition. Wear behaviour of the alloy in the cast condition is superior to the homogenized condition, though cast structure exhibit low hardness compared to the other. This is attributed to the easy crack propagation along the CuAl₂ precipitates in the homogenized condition, compared to the grain boundary in the as-cast structure. Wear properties of the resultant composite are superior to the alloy. Effect of particulate composition is studied by varying the copper concentration between 5 and 15 wt%. Composites with high copper content exhibit better wear resistance than the dilute ones, which is attributed to the increased hardness due to large population of intermetallics.     

聚四苯基卟啉及其金属配合物的XPS研究

用XPS 研守了聚四苯基卟啉及其18 种金属化合物, 证实了这些金属化合物为金属配合物. 由π→π* 激发能, 跃迁几率和N18 位移证明这些金属化合物是金属离子镶嵌在芳族大π体系共轭环中而成的金属配合物. 初步表明这些金属配合物的稳定性金属原子半径的增大而降低.     

稀土(III)-冠醚配位反应的热力学性质I:稀土(III)高氯酸盐与苯-15-冠-5-在乙腈溶液中配位反应的量热滴定研究

用量热滴定法于298.15K测定了除钪、钷以外的全部十五种稀土(III)高氯酸盐与苯并-15-冠-5在乙腈溶液中的配位作用。借助计算机算出了配合物的稳定常数和配位焓, 进而算出了配位自由能和配位熵。结果表明:十五种稀土(III)离子与苯并-15-冠-5都可以配位, 配位焓为正值;La^3^+配合物最稳定, Ce^3^+次之, 其余稀土(III)离子配合物稳定性变小, 但彼此差别不大, 在Tb处有突变;熵在配合物形成时起稳定化作用。     

聚醚型非离子表面活性剂的混合表面膜III, 环氧乙烷一环氧丙烷嵌段共聚物, 聚丙二醇与十六醇, 硬脂酸的二元混合物

本文进一步研究了环氧乙烷-环氧丙烷嵌段共聚物(L61和F68)、聚丙二醇(PPG)分别与十六醇(CA)、硬脂酸(SA)所形成的二元混合膜。根据对π-α实验结果的分析, 表明PPG-CA、PPG-SA、F68-SA和L61-SA的混合单分子膜是不相混溶的, 而L61-CA和F68-CA的混合单分子膜则是混溶的。     

烯烃配位的过渡金属卡宾配合物的研究XVI:四氟苯并双环[2,2,2]辛三烯三羰基铁的新奇开环反应-新型螯合双烯丙基三羰基铁配合物的合成和结构

四氟苯并双环[2,2,2]辛三烯三羰基铁(C12H6F4)-Fe(CO)3(1)与芳基锂试剂ArLi(Ar=C6H5、o-, m-, p-CH3C6H4、p-CH3OC6H4、p-CiC6H4), 在低温下反应, 生成的酰羰基锂盐中间体用三乙基氧 -四氟硼酸盐(Et3OBF4)在水溶液中于0℃进行烷基化时, 双环烯烃配体开环, 生成组成为(C12H6F4)(CO)2FeC(OC2H5)Ar的螯合双烯丙基二羰基铁配合物(2-7), 配合物5的晶体属单斜晶系, 晶胞参数为;a=16.870(4), b=13.707(4), c=19.361(4)A, β=107.92(2)°.V=4259(1)A^3, Z=8, 空间群为C^62h-C2/c, 最后的偏离因子R=0.0409, Rw=0.0391。     

电活性质点Fe^2^+离子在六氰亚铁钒薄膜中的传输

电活性质点Fe^3^+可穿透六氰亚铁钒薄膜在玻璃碳基体电极表面于较负电位处直接氧化, 也可经VHF膜中氧化还原点位的媒介在较正电位处理膜-溶液界面及膜内部发生催化氧化. 两个过程分别在用VHF修饰过的旋转GC电极上的伏安曲线中产生, 可明确分辨的第一波和第二波. 第一波的极限电流受Fe^2^+离子在溶液中和膜中的扩散速率控制.VHF薄膜对Fe^2^+离子的透过能力, kDm/d, 为10^-^3-10^-^2cm.s^-^1数量级, 随膜厚度增大而减小, 不随溶液中Fe^2^+离子浓度改变.     

N-乙酰基-N-苯酰基二茂铁基腙的IIB族和主族金属螯合物

本文报道了N-乙酰基-N-苯酰基二茂铁基腙[Fe-C(CH3)=NNH-COC6H5,Fc=C5H5FeC5H4]的IIB族和某些主族金属螯合物.