Ring‐opening polymerization of lactones initiated by diphenylzinc–coinitiator systems

Diphenylzinc, alone or in combination with water and butanone as coinitiators, was used as a polymerization initiator system for a variety of lactones at varying temperatures. The resulting data indicate that the course of the polymerization is greatly influenced by the lactone structure, as well as by the molar ratio of coinitiator to diphenylzinc. When used alone, diphenylzinc exhibited high activity as an initiator in δ‐valerolactone polymerizations, although it was less efficient when used in the β‐butyrolactone and the β‐propiolactone polymerizations. Activity in the polymerization of β‐lactones was increased by adding small amounts of butanone or water. It was also observed that the diphenylzinc–butanone combination was more effective than the diphenylzinc–water mixture in the polymerizations of β‐butyrolactone and β‐propiolactone. Copyright © 2003 Society of Chemical Industry     

Biotransformation of l‐menthol by twelve isolates of soil‐borne plant pathogenic fungi (Rhizoctonia solani) and classification of fungi

The microbial transformation of l‐menthol ( 1 ) was investigated by using 12 isolates of soil‐borne plant pathogenic fungi, Rhizoctonia solani (AG‐1‐IA Rs24, Joichi‐2, RRG97‐1; AG‐1‐IB TR22, R147, 110.4; AG‐1‐IC F‐1, F‐4, P‐1; AG‐1‐ID RCP‐1, RCP‐3, and RCP‐7) as a biocatalyst. Rhizoctonia solani F‐1, F‐4 and P‐1 showed 89.7–99.9% yields of converted product from 1 , RCP‐1, RCP‐3, and RCP‐7 26.0–26.9% and the other isolates 0.1–12.0%. In the cases of F‐1, F‐4 and P‐1, substrate 1 was converted to (?)‐(1S,3R,4S,6S)‐6‐hydroxymenthol ( 2 ), (?)‐(1S,3R,4S)‐1‐hydroxymenthol ( 3 ) and (+)‐(1S,3R,4R,6S)‐6,8‐dihydroxymenthol ( 4 ), which was a new compound. Substrate 1 was converted to 2 and/or 3 by RRG97‐1, 110.4, RCP‐1, RCP‐3 and RCP‐7. The structures of the metabolic products were elucidated on the basis of their spectral data. In addition, metabolic pathways of the biotransformation of 1 by Rhizoctonia solani are discussed. Finally, from the main component analysis and the differences in the yields of converted product from 1 , the 12 isolates of Rhizoctonia solani were divided into three groups based on an analysis of the metabolites. Copyright © 2003 Society of Chemical Industry     

TEM Studies of High Temperature Corrosion Behaviour of TiAl Intermetallics with Surface Modifications

The oxidation/sulphidation behaviour of a Ti‐46.7Al‐1.9W‐0.5Si alloy with a TiAl₃ diffusion coating was studied in an environment of H₂/H₂S/H₂O at 850^oC. The kinetic results demonstrate that the TiAl₃ coating significantly increased the high temperature corrosion resistance of Ti‐46.7Al‐1.9W‐0.5Si. The SEM, EDX, XRD and TEM analysis reveals that the formation of an Al₂O₃ scale on the surface of the TiAl₃‐coated sample was responsible for the enhancement of the corroison resistance. The Ti‐46.7Al‐1.9W‐0.5Si alloy was also modified by Nb ion implantation. The Nb ion implanted and as received sampels were subjected to cyclic oxidation in an open air at 800^oC. The Nb ion implantation not only increased the oxidation resistance but also substantially improved the adhesion of scale to the substrate.     

Wear and Creep Characteristics of a Carbon‐Derived Si3N4/SiC Micro/Nanocomposite

In the presented work some properties of a recently developed Si₃N₄/SiC micro/nanocomposite have been investigated. The material was tested using a pin on disc configuration. Under unlubricated sliding conditions using Si₃N₄ pin at 50 % humidity, the friction coefficient was in the range of 0,6 ‐ 0,7. The reduction of humidity resulted in a lower coefficient of friction, in vacuum the coefficient of friction had a value of about 0,6. The wear resistance in vacuum was significantly lower then that in air. The wear patterns on the Si₃N₄+SiC disc revealed that mechanical fracture was the wear controlling mechanism. Creep tests were realized in four point bending configuration in the temperature interval 1200‐1400 °C at stresses 50,100 and 150 MPa and the minimal creep deformation rate was established for each stress level. The activation energy, established from the minimal creep deformation had a value of about 360 kJ/mol and the stress exponent values were in the range of 0.8‐1.28. From the achieved stress exponents it can be assumed that under the studied load/temperature conditions the diffusion creep was the most probable creep controlling mechanism.     

Dissolved organic carbon dynamics in the upper rhone: The influence of side-arms?

Dissolved organic carbon (DOC) dynamics were investigated over a two year period in the Upper Rhǒne River to examine the role of side-arms in providing DOC to the main channel in relation to discharge fluctuations, especially floods. Concentrations of DOC are shown to remain low in space and in time (average 1.5 mg ^?1) and to be more related to global hydrological events (precipitation) than to any local flushing for backwaters during floods. The results do not support the general assumption that side-arms are the providers of DOC to the main channel.     

中国古典园林三维造型研究

论述了采用层次结构化及参数化三维造型方法，建立一个以造型函数库为核心，从而构造各类、各级园林景观构件表面模型的方法和过程。对于某些非建筑类的园林配景构件，采用了Ｆｒａｃｔａｌ方法进行造型。     

冲裁模CAD／CAM结构库之原型法

本文首先给出了一种新的2.5D 实体表示法,然后在此基础上提出了“原型”的概念。原型法的思想运用在结构库的管理中主要体现在它将模具结构与构成这种结构的零件之间的强联系变成弱联系,结构库面向的对象是一个具有整体性和可运算性的结构原型。这样的原型结构库基本上达到了通用性与开放性的要求。     

HPMBP与伯胺N_(1923)对希土元素(Ⅲ)的协同萃取

本文研究了HPMBP与伯胺N_(1923)的二甲苯溶液,从盐酸介质中协同萃取希土(Ⅲ)的机理。用斜率法、恒摩尔法确定了协萃配合物的组成为:RNH_3Ln(PMBP)_4。求得关于Pr(Ⅲ)协萃反应的平衡常数及协萃配合物的生成常数分别为:logK_(12)=-1.95;logβ_(12)=3.94。实验发现,协萃系数(R)随希土元素的原子序数(Z)递变而呈现“双峰效应”。还研究了协萃配合物的IR,NMR谱。     

Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry