Studies on high density polyethylene (HDPE) functionalized by ultraviolet irradiation and its application

The structure and properties of high density polyethylene (HDPE) functionalized by ultraviolet irradiation at different light intensities in air were studied by electron analysis, FTIR spectroscopy, contact angle with water, differential scanning calorimetry and mechanical properties measurement. The results show that oxygen‐containing groups such as C?O, C—O and C(?O)O were introduced onto the molecular chain of HDPE following irradiation, and the rate and efficiency of HDPE functionalization increased with enhancement of irradiation intensity. After irradiation, the melting temperature, contact angle with water and notched impact strength of HDPE decreased, the degree of crystallinity increased, and their variation amplitude increased with irradiation intensity. Compared with HDPE, the yield strength of HDPE irradiated at lower light intensity (32 W m^?2 and 45 W m^?2) increases monotonically with irradiation time, and the yield strength of HDPE irradiated at higher light intensity (78 W m^?2) increases up to 48 h and then decreased with further increase in irradiation time. The irradiated HDPE behaved as a compatibilizer in HDPE/polycarbonate (PC) blends, and the interface bonding between HDPE and PC was ameliorated. After adding 20 wt% HDPE irradiated at 78 W m^?2 irradiation intensity for 24 h to HDPE/PC blends, the tensile yield strength and notched Izod impact strength of the blend were increased from 26.3 MPa and 51 J m^?1 to 30.2 MPa and 158 J m^?1, respectively. Copyright © 2003 Society of Chemical Industry     

Dynamical considerations of network properties

Elasticity is discussed as an aspect of viscoelasticity, which is described by the tube model. The effects of both crosslinks and entanglements contribute to this model and a discussion of how these effects can be quantified is given. At high enough concentration, entanglements ensure the existence of elastic effects even without crosslinks, and a theory is presented on how this dynamical phase change comes about.     

Network topology and the theory of rubber elasticity

The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters.     

Potential of vibro-milling technique for preparation of electroceramic nanopowders

The potential of the vibro-milling technique as a simple method to obtain usable quantities of single-phase electroceramic powders with nanosized particles was examined. A detailed study considering the role of both milling time and firing condition on phase formation and particle size of the final product was performed. The calcination temperature for the formation of the desired phase was lower when longer milling times have been applied. More importantly, by employing an appropriate choice of the milling time and calcination condition, high purity electroceramic nanopowders have been successfully prepared with a simple solid-state reaction method.     

Hydrothermal Reaction Mechanism and Pathway for the Formation of K2Ti6O13 Nanowires

Calculations and detailed first principle and thermodynamic analyses have been performed to understand the formation mechanism of K₂Ti₆O₁₃ nanowires (NWs) by a hydrothermal reaction between bulk Na₂Ti₃O₇ crystals and a KOH solution. It is found that direct ion exchange between K⁺ and Na⁺ plus H⁺ interactions with [TiO₆] octahedra in Na₂Ti₃O₇ promote the formation of an intermediate H₂K₂Ti₆O₁₄ phase. The large lattice mismatch between this intermediate phase and the bulk Na₂Ti₃O₇ structure, and the large energy reduction associated with the formation of this intermediate phase, drive the splitting of the bulk crystal into H₂K₂Ti₆O₁₄ NWs. However, these NWs are not stable because of large [TiO₆] octahedra distortion and are subject to a dehydration process, which results in uniform K₂Ti₆O₁₃ NWs with narrowly distributed diameters of around 10 nm.     

在酸性介质中N-H伪酸Mannich反应机理的量子化学研究

用量子化学中的ＳＣＦ－ＭＯＡＭ１方法，全优化计算了以苯并唑酮为伪酸组分的（Ｎ－Ｈ酸）Ｍａｎｎｉｃｈ反应的反应物、过渡态和产物络合物的分子几何构型、电子结构和生成热。根据计算所得各反应的活化能，提出了该反应在酸性介质中的机理，即甲醛首先与苯并唑酮作用，其产物再与二甲胺作用生成Ｍａｎｎｉｃｈ碱，并就其缘由进行了讨论。     

Some factors affecting the electrical properties of carbon-black-loaded butyl rubber during vulcanization

Butyl rubber mixtures loaded with 70 phr general purpose furnace black (GPF) and tetramethyl thiuram disulphide (TMTD)/S as vulcanizing system were prepared. The kinetics of their electrical conductivity development during the vulcanization process were followed by using an especially devised system. It was found that the increase in the electrical conductivity during vulcanization obeys an exponential growth function with time constant τ, which markedly decreases with increasing vulcanization temperature as well as with the efficiency of the vulcanizing system. After completion of the vulcanization process, about 80 min, the samples obtained possess reasonable stability and reproducibility of electrical conductivity.     

新取代苯基荧光酮试剂的合成及其性质的研究Ⅱ．新型取代苯基荧光酮与金属离子显色反应的研究

研究了３，５－二溴－４－氨基苯基荧光酮、３，５－二溴－４－偶氮变色酸等８种苯基荧光酮在酸性介质中与高价金属离子Ｚｒ（Ⅳ）、Ｍｏ（Ⅵ）、Ｗ（Ⅵ）、Ａｌ（Ⅲ）、Ｇａ（Ⅲ）等的显色反应。３，５－位二溴取代的试剂的灵敏度高于未取代的灵敏度，摩尔吸光系数绝大多数在１０５Ｌ·ｍｏｌ－１·ｃｍ－１以上。     

Stabilization of bioethanol recovery with silicone rubber‐coated ethanol‐permselective silicalite membranes by controlling the pH of acidic feed solution

In order to produce highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, techniques to suppress adsorption of succinic acid, which is a chief by‐product of ethanol fermentation and causes the deterioration in pervaporation performance, onto the silicalite crystals was investigated. The amount adsorbed increased as the pH of the aqueous succinic acid solution decreased. The pervaporation performance also decreased with decreasing pH when the ternary mixtures of ethanol/water/succinic acid were separated. Using silicalite membranes individually coated with two types of silicone rubber, pervaporation performance was significantly improved in the pH range of 5 to 7, when compared with that of non‐coated silicalite membranes in ternary mixtures of ethanol/water/succinic acid. Moreover, when using a silicalite membrane double‐coated with the two types of silicone rubber, pervaporation performance was stabilized at lower pH values. In the separation of bioethanol by pervaporation using the double‐coated silicalite membrane, removal of accumulated substances having an ultraviolet absorption maximum at approximately 260 nm from the fermentation broth proved to be vital for efficient pervaporation. Copyright © 2005 Society of Chemical Industry