Hydrolysis-condensation of tetraethoxysilane in nonparental solvents studied by GC-MS

Gas-chromatography coupled with mass spectrometry was used to investigate the hydrolysis and condensation of tetra-ethoxysilane (TEOS) in nonparental solvents (MeOH and nPrOH). In the presence of nonparental solvents, the reaction that advanced at highest rate is alkoxy group scrambling, that changes the precursor at the molecular level. Subsequent stages of hydrolysis-polycondensation process are essentially determined by the reactivity of the new molecular species formed.     

Influence of concentration on the activation energy for diffusion in polymer-solvent systems

The self-diffusion of benzene, toluene, and ethylbenzene in polystyrene have been analyzed using the Vrentas/Duda free-volume diffusion model. Diffusion coefficient predictions suggest an exponential concentration dependence of the activation energy required to overcome attractive forces, E. Without the use of any diffusion data approximating E as zero over the entire concentration range yields self-diffusion coefficient predictions which are in good agreement with experimental data. © 1992 John Wiley & Sons, Inc.     

Reagent concentration effects in the REM resin solid phase synthesis of tertiary amines

The use of reagent concentration has resulted in increased rates for all stages of the REM resin synthesis of tertiary amines. These increases in rate translate into faster reaction times, higher yields and lower reagent consumption. Of the methods examined, the most successful was the use of perfluorous solvents, either alone or with a small amount of organic co-solvent.     

On the growth strain origin and stress evolution prediction during oxidation of metals

High temperature oxidation of metals leads to residual stresses in the metal and in the oxide. In this work, we try to predict the evolution of the residual stresses in the growing oxides layers, during isothermal oxidation. The origin of these stresses is based on the microstructural model of Clarke, however, another justification is proposed, assuming a proportional dependence of the growth strain with the oxide layer thickness. Using the mechanics of thin layers, as well as the analysis proposed to describe the growth strain, a system of equations are deduced that predict the stresses evolution with oxidation time. Numerical analysis is performed, leading to a set of theoretical curves.     

SIMS analysis of residual gas elements with a Cameca IMS-6f ion microprobe

In this paper, we present experimental data for SIMS analysis of residual gas elements (RGEs) with a Cameca IMS-6f ion microprobe. We considered a simple experimental technique, which provides an effective separation of the secondary ions, sputtered from the bulk of a target, and from the molecules, adsorbed on the analyzed surface from the residual atmosphere. The technique needs the sputtering yield of one monolayer (ML) per second to be applied. The method improves (in more than one order of magnitude) the detection limit for RGEs in SIMS analysis, and simultaneously, provides information about the residual atmosphere at the sample surface and in the main chamber of the experimental instrument. The method provides a calibration method for an ion gauge, and can be used for SIMS analysis with a gas (O₂) flooding.     

有机溶剂化效应对多元配合物显色反应作用的研究 Ⅰ.有机溶剂对 M-CAS-CTMAB 体系显色反应微环境影响之初探

本文研究了有机溶剂加入后,表面活性剂增敏型体系微环境的变化。用核磁共振方法确定了有机溶剂分子与CTMAB胶束分子的作用部位。通过CTMAB溶液电导率测定及c.m.c值的测定,发现有机溶剂加入确实形成了一种新胶束。还研究了有机溶剂对显色反应速度的影响。并考察了体系微环境变化与相应显色液吸光度值的关系。我们的实验初步表明,有机溶剂的存在,改变了原有的CTMAB胶束,是增敏作用的重要因素,因而改变了发生显色反应的微环境。     

高强度高电导率聚乙炔的合成——醚类溶剂的结构对性能的影响

通过选用不同醚类结构做溶剂加热回流Ti(OBu)_4-AIEt_3催化剂,并采用非溶剂聚合方法进行乙炔聚合发现,所得HPPA膜的强度和电导率都有了较大提高。其中直链醚制得的PA膜强度(抗张强度大于100MPa)和空气稳定性比用环醚得到的PA膜高得多,但用前者时的乙炔聚合速率远低于后者。两体系得到的HPPA膜的碘掺杂电导率值相近(～10~3S/cm),拉伸后可达10~4S/cm量级。SEM、TEM及IR光谱的结果表明,不同醚制得的PA膜的纤维束直径及顺式含量有较大差别。     

减压渣油供氢剂减黏裂化研究

减黏裂化作为一种不生成焦炭的热加工方法主要涉及两类化学反应，裂解反应和缩合反应。裂解反应使减压渣油的平均分子量及其胶团直径变小，改善渣油的倾点和黏度；缩合反应使减压渣油及其中间产物中的芳烃、烯烃等缩合成大分子量产物，产生新的胶核，甚至生成焦炭。常规减黏裂化过程中，这两类化学反应主要与反应温度和反应时间有关。在热作用下渣油中的大分子裂解为H／C原子比相对较高的饱和烃自由基和H／C原子比相对较低的芳香性自由基。后者还可失去自身的环烷氢而使其H／C原子比进一步降低。如果体系中有足量的氢化芳烃存在，那么氢化芳烃分子上的活泼氢就可能转移到芳香性自由基的单电子位，将自由基封闭，从而阻止芳香性自由基之间的相互缩合，抑制使分子长大的缩合反应。如果体系中的氢化芳烃含量不足。则热反应体系中就没有足够的活泼氢将芳香性自由基封闭，芳香性自由基缩合反应的几率较高，造成过早地生焦。这种来自渣油分子自身的活泼氢的化学行为与渣油热反应生焦诱导期有一定关系。     

Diffusion in organic solvents: Interdiffusion coefficient of 1,1,2,2-tetrabromoethane

Interdiffusion coefficient have been measured for 1,1,2,2-tetrabromoethane in 21 organic solvents in order to ascertain the influence of shape, size, viscosity, nature and degree of branching, of the solvent molecules on transport properties. None of the existing correlations for diffusion in binary liquid systems appear to fit all the experimental data. Steric effects due to the solvent molecules are shown to be very important in the interpretation of the diffusion process.