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.     

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。     

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     

Catalytic properties and electronic structure of copper ions in Cu-ZSM-5

The effect of ion exchange conditions, such as Si/Al ratio, precursor copper salt, pH and concentration of the solution, on the catalytic activity in SCR of NO by propane and on the electronic state of copper ions in Cu-ZSM-5 has been studied. The NO conversion in NO SCR by C₃H₈ has been found to reach a maximum value at Cu/Al ratio about 0.37–0.4 and remain constant at higher Cu/Al.

ESR and UV–vis DR spectroscopy have been used to elucidate stabilization conditions of copper ions in Cu-ZSM-5 zeolites as isolated Cu²⁺ ions, chain copper oxide structures and square-plain oxide clusters. The ability of copper ions for reduction and reoxidation in the chain structures may be responsible for the catalytic activity of Cu-ZSM-5. These transformations of copper ions are accompanied by the observation of intervalence transitions Cu²⁺–Cu⁺ and CTLM of the chain structures in the UV–vis spectra.     

Transmittance and cathodoluminescence of AlN ceramics sintered with Ca3Al2O6 as sintering additive

Aluminum nitride ceramics were prepared by sintering with 0–4.8 mass% of Ca₃Al₂O₆ (C₃A) as a sintering additive. The transmittance in the range of 260–550 nm increased with increasing amount of C₃A. The cathodoluminescence intensity attributed to oxygen-induced defects decreased with increasing amount of C₃A. From the results, the increase of the transmittance in the range of 260–550 nm was considered to be related to the decrease of the oxygen-induced defect density.     

Epoxy paint failure in B-52 fuel tanks: Part II. Influence of DIEGME concentration in the fuel on the failure process

A model has been proposed to explain the failure of the original BMS10-39 epoxy paint on upper vertical surfaces in B-52 fuel tanks. The model involves interaction of the paint with DIEGME, a fuel system ice inhibitor (FSII) in jet fuel, that is distilled from the liquid fuel. In this communication, distillation experiments used to support the model are refined to better match the mass transfer of vapor from fuel in a B-52 fuel tank at close to room temperature. The interaction of these lower temperature distillates with the paint affirms the earlier model. On the basis of these experiments it is proposed that paint failure may be controlled or eliminated by reducing the level of DIEGME in the fuel. Proposed changes in military jet fuel composition are detailed.