Kinetics of chlorination of tantalum pentoxide in mixture with sucrose carbon by chlorine gas

The mechanism and kinetics of β-Ta₂O₅ chlorination, mixed with sucrose carbon, have been studied by a thermogravimetric technique. The investigated temperature range was 500 °C to 850 °C. The reactants and reaction residues were analyzed by scanning electronic microscopy (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller method for surface area (BET). The effect of various experimental parameters was studied, such as carbon percentage, temperature, chlorine partial pressure, and flow, use of the multiple sample method, and carbon previous oxidation. The carbon percentage and previous treatment have an effect on the system reactivity. The temperature has a marked effect on the reaction rate. In the 500 °C to 600 °C temperature interval, the apparent activation energy is 144 kJ/mol of oxide, while at higher temperatures, the activation energy decreases. With high chorine partial pressures, the order of reaction is near zero. The kinetic contractile plate model, X=kt, considering carbon oxidation as the controlling stage, is the one with the best fit to the experimental data. A probable mechanism for the carbochlorination of β-Ta₂O₅ is proposed: (1) activation of chlorine on the carbon surface, (2) chlorination of Ta₂O₅, (3) oxidation of carbon, and (4) recrystallization of β-Ta₂O₅.     

Web-based systems design: a study of contemporary practices and an explanatory framework based on “method-in-action”

This paper reports the findings of a detailed study of Web-based systems design (WBSD) practices in Ireland based on data collected over a 3-year period (2002–2005), the objectives of which were to (1) contribute towards a richer understanding of the current “real-world” context of WBSD by characterising the profile of a typical project (team size, timeframe, nature of requirements, etc.) and identifying the key challenges, constraints, and imperatives (i.e. “mediating factors”) faced by Web-based system designers, and (2) understand how those contextual parameters and mediating factors influence the activity of WBSD as regards the selection and enactment of whatever design practices are therefore engaged (i.e. the use of methods, procedures, etc.). Data was gathered through a survey which yielded 165 usable responses, and later through a series of semi-structured qualitative interviews. Using grounded theory, an explanatory conceptual framework is derived, based on an extension of the “method-in-action” model, the application of which to WBSD has not been previously investigated in depth. It is proposed that this framework of WBSD issues is valuable in a number of ways to educators, researchers, practitioners, and method engineers.     

Development of a new advanced process for manufacturing polyacetal resins. Part III. End-capping during polymerization for manufacturing acetal homopolymer and copolymer

Conventionally, acetal homopolymer or copolymer is obtained by the polymerization of formaldehyde or trioxane, following the end-capping using acetic anhydride or unzipping of the unstable polymer end fraction. First, Asahi Chemical developed a new process to obtain an end-capped polymer during polymerization of highly purified formaldehyde using acetic anhydride as the chain-transfer agent. Use of highly purified formaldehyde and endcapping during polymerization using acetic anhydride as a chain-transfer agent or an endcapping agent will provide a simple process for manufacturing acetal homopolymer. The polymerization mechanism was confirmed by infrared spectroscopy analysis and proton NMR analysis of the polymer obtained. Second, for the acetal copolymer, purified trioxane was copolymerized with ethylene oxide in the presence of methylal, which gave an endcapped polymer with high thermal stability. Two new intermediates from the initiation reaction of the copolymerization, 1,3,5,7-tetraoxacyclononane (TOCN) and 1,3,5,7,10-pentaoxacyclododecane (POCD), were isolated and a new initiation mechanism was proposed. © 1993 John Wiley & Sons, Inc.     

Excessive closure of the right eye: a new sign of infarction in the territory of the ipsilateral right middle cerebral artery

In right middle cerebral territory infarction a new sign, excessive closure of the right eye ipsilateral to the lesion and mild closure of the left eye on command, was noted. The excessive ipsilateral eye closure was not observed on spontaneous eye closure.