Formation and inhibition of free radicals in electrically stressed and aged insulating polymers

Previous work has shown that prebreakdown, electrical aging, and breakdown phenomena are directly associated with charge carriers injected from electrical contacts and their subsequent dissociative trapping and recombination. In addition, the energy released from each trapping or recombination event is dissipated in the breaking of the bonds of macromolecules, thus forming free radicals and new traps in the electrically stressed insulating polymers, as predicted by Kao's model. It is this gradual degradation process that leads to electrical aging and destructive breakdown. New experimental results are presented to confirm previous findings and a new approach to inhibit the degradation process by the incorporation of suitable dopants into the polymer. The concentration of free radicals in the polymer increases with an increasing electric field at a fixed stress time of 250 h and with increasing stress time at a fixed electric field of 833 kV cm^?1. The concentration of free radicals is directly related to the concentration of new traps created by stress. However, when suitable dopants are incorporated, the initiation voltage for the occurrence of electrical treeing and the breakdown strength are both increased. The dopants tend to create shallow traps and have little effect on the deep trap concentration. This implies that the dopants act as free‐radical scavengers that tend to satisfy the unpaired electrons of the broken bonds, which create new acceptor‐like electron traps and new shallow traps. By doing so, the shallow traps screen the deep traps, thereby reducing the energy released during trapping and recombination and the probability of breaking the macromolecular bonds and causing structural degradation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3416–3425, 2003     

Pack cementation process for the formation of refractory metal modified aluminide coatings on nickel-base superalloys

The vapour phase compositions of a series of pack powder mixtures containing elemental Al and Hf or W powders as depositing sources and CrCl₃·6H₂O or AlF₃or CrF₃as activators were analysed in an attempt to further develop the pack cementation process to codeposit Al and Hf or W to form diffusion coatings on nickel base superalloys. The results suggested that Al could be codeposited with Hf, but not with W, from the vapour phase. Compared with both AlF₃and CrF₃, CrCl₃·6H₂O has been shown to be a more suitable activator for codepositing Al with Hf. The optimum coating temperature was identified to be in the range of 1050°C to 1150°C. Based on the thermochemical analysis, a series of coating deposition studies were undertaken, which confirmed that codeposition of Al and Hf could be achieved at a deposition temperature of 1100°C in the CrCl₃·6H₂O activated packs containing elemental Al and Hf powders. The coating obtained had a multilayer structure consisting of a Ni₇Hf₆Al₁₆top layer and a NiAl layer underneath, followed by a diffusion zone, which revealed that the coating was formed by the outward Ni diffusion. It is suggested that the compositions suitable for codeposition of Al and Hf could be effectively identified by comparing the vapour pressures of HfCl₄and HfCl₃with that of AlCl in the packs activated by chloride salts. It has also been experimentally demonstrated that, although W could not be deposited from the vapour phase, a high volume of fine W particles can be entrapped into the outer NiAl coating layer formed by the outward Ni diffusion using a modified pack configuration. This leads to the formation of a composite coating layer with W particles evenly distributed in a matrix of NiAl. It is suggested that this modified pack process could be similarly applied to develop nickel aluminide coatings containing other refractory metals that may not be codeposited with Al from the vapour phase.     

Analysis of the Scattering Characteristic of Several Waveguide Components Using Boundary Element Method

Several kinds of waveguide components such as curved waveguide bends, arbitrary angle waveguide bends and T-junctions have been analyzed with boundary element method in this paper. A new discretization method for the boundary element method to solve the waveguide discontinuities has been given. The numerical results obtained agree well with the experimental results and numerical results in other literature. Especially, the scattering characteristics of Forded E-, H-plane T-junctions in 3mm band have been analyzed using boundary element method and the calculation results are presented.     

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.     

Fatigue crack growth in SiC particulates reinforced Al matrix graded composite

The SiC/Al graded composite was fabricated by powder metallurgy processing and its fatigue crack growth behavior was studied. The volume percentage of SiC particulates was distributed from 5 to 30% layer by layer on the cross section. Since the aluminium was dissolved together, there was no evident interface between the two layers with different volume fraction of SiC particulates. Fatigue crack growth was in direction of from 5 to 30% SiC layers under sinusoidal wave-form. The retardation of fatigue crack growth was found when crack propagated from low volume fraction of SiC to high volume fraction of SiC. The crack deflection and branching between two layers were observed, which decreased crack growth rates. In view of crack tip driving force, the plasticity mismatch between the layers shielded crack tip driving force, i.e. decreased the effective J-integral at the tip of the crack as the plastic zone of the crack tip spread from the weaker material into the stronger material.     

Thermomechanical finite-element model of shell behavior in continuous casting of steel

A coupled finite-element model, CON2D, has been developed to simulate temperature, stress, and shape development during the continuous casting of steel, both in and below the mold. The model simulates a transverse section of the strand in generalized plane strain as it moves down at the casting speed. It includes the effects of heat conduction, solidification, nonuniform superheat dissipation due to turbulent fluid flow, mutual dependence of the heat transfer and shrinkage on the size of the interfacial gap, the taper of the mold wall, and the thermal distortion of the mold. The stress model features an elastic-viscoplastic creep constitutive equation that accounts for the different responses of the liquid, semisolid, delta-ferrite, and austenite phases. Functions depending on temperature and composition are employed for properties such as thermal linear expansion. A contact algorithm is used to prevent penetration of the shell into the mold wall due to the internal liquid pressure. An efficient two-step algorithm is used to integrate these highly nonlinear equations. The model is validated with an analytical solution for both temperature and stress in a solidifying slab. It is applied to simulate continuous casting of a 120 mm billet and compares favorably with plant measurements of mold wall temperature, total heat removal, and shell thickness, including thinning of the corner. The model is ready to investigate issues in continuous casting such as mold taper optimization, minimum shell thickness to avoid breakouts, and maximum casting speed to avoid hot-tear crack formation due to submold bulging.     

Glycoconjugated polymer 6. Synthesis of poly[styrene-<Emphasis Type="Italic">block</Emphasis>-(styrene-<Emphasis Type="Italic">graft</Emphasis>-amylose)] via potato phosphorylase-catalyzed polymerization

Summary The potato phosphorylase-catalyzed polymerization of α-D-glucose-1-phosphate (G-1-P) onto poly[styrene-block-(4-vinylbenzyl maltohexaoside)] (1) was performed at the molar ratios of [G-l-P]₀ and [maltohexaose]₀ of 35, 80, and 250. The product was found to be soluble in dimethyl sulfoxide, which was a good solvent for amylose, and showed the complex-formation with iodine, indicating that the product was assignable to poly[styrene-block-(styrene-graft-amylose)] (2). The quantitative analysis of the liberated phosphoric acid gave the average degree of polymerization o f the glucose unit (n) as 27, 5 1, and 180 for 2-I, 2-II, and 2-III, respectively. Received: 29 November 2002/Accepted: 22 December 2002 Correspondence to Toyoji Kakuchi