Kinetics of hydantoin formation

The reaction of lignite in a slagging gasifier produces reactants which in turn form 5,5-dimethylhydantoin (DMH) as a major constituent in the condensate water. Variations in plant operating conditions made it impossible to accurately study the kinetics of formation of DMH in the actual gasifier water, and thus a model system was chosen. The reaction of acetone cyanohydrin in the presence of excess ammonium carbonate at concentrations approaching those obtained in the condensate water were studied at 50,70, and 90 °C. Secondorder kinetics were obeyed, and the pseudo second-order rate constants at the respective temperatures were 1.86, 3.6, and 4.62 dm³ mol^{? 1} h^{? 1}. Independent variation of the concentration of either acetone, cyanide, ammonia or carbonate gave results consistent with the interpretation that the formation of DMH is first order in all reactants: rate of formation of DMH = k[acetone][HCN][NH₃][CO₂]. The pseudo second-order rate constant is a complex rate constant including several rapid equilibria. A mechanism consistent with the kinetic data is presented.     

Effect of polymerization conditions on the melt rheological properties of vinyl chloride–vinyl acetate copolymers

Mathematical models have been developed which predict the composition, molecular weight, and melt rheological properties for vinyl chloride/vinyl acetate copolymers of inherent viscosity range 0.4–0.7 dL/g and bound vinyl acetate levels of 3.8–17.4%. The effect of polymer long chain branching on the viscous/elastic moduli ratio is discussed as well as the comparison of Tinius–Olsen melt index measurements vs. mechanical spectrometer results. The reactivity ratio for vinyl chloride/vinyl acetate comonomer pairs was remeasured and found to be significantly different from literature values.     

Particle structure of PVC based on cellulosic suspension system. III. Effect of monomer refluxing

The effects of monomer refluxing on both resin properties and reactor fouling of suspension PVC have been studied in a laboratory-scale 14-L reactor. Process control equations were developed which related the particle properties to the reflux condenser operation by controlling the parameters of (1) the time at which refluxing is begun and (2) the rate profile of heat removal from the condenser. An operating envelope has been developed for laboratory scale operations which optimizes the cycle time of polymerization while minimizing the adverse effects on particle properties. These operating conditions may have application to production scale operations when the proper scaling factors are employed.     

Contacting modes and behaviour classification of gas—solid and other two-phase suspensions

An attempt is made to extend schemes for classifying the behaviour of gas—solid contacting modes and other two-phase systems. The regime diagram approach of Reh (1971) is modified and extended to cover the operating regions of common reactors and contactors where a gas flows upwards through a bed of solids including fixed and moving packed beds, conventional fluidized beds, circulating beds, spouted beds, and pneumatically conveyed suspensions. New boundaries are proposed between groups A and B and between groups B and D of the Geldart (1972, 1973) powder classification scheme. These boundaries reflect more recent data and allow the classification scheme to be used for gases other than air and for temperatures and pressures other than atmospheric.     

Modeling and optimization of fringe capacitance of nanoscale DGMOS devices

We analyze the impact of gate electrode thickness and gate underlap on the fringe capacitance of nanoscale double-gate MOS (DGMOS) transistors. We propose an analytical fringe capacitance model considering gate underlap and finite source/drain length. A comparison with the simulation results show that the model can accurately estimate the fringe capacitance of the device. We show that an optimum gate underlap can significantly reduce the fringe capacitance resulting in higher performance and lower power consumption. Also, the effects of process variation in gate underlap devices are discussed. Simulation results on a three-stage ring oscillator show that with optimum gate underlap 32% improvement in delay can be achieved.     

Clinical psychologists reflect on the usefulness of various components of graduate training.

Graduates of clinical training programs were surveyed to determine the degree to which they have found various graduate school experiences useful in their professional work. Samples of academic clinical psychologists and practicing clinical psychologists reported time allocation and preference for various professional activities, perceived usefulness of various theoretical orientations, and the influence on their current professional work of 19 different graduate training topics. Results suggest that where differences exist, academic clinical psychologists are generally more satisfied with Boulder-model-inspired scientific training than are clinical practitioners. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Experimental abatement data of underflow baffles for removal of floatables in the CSOs of the Greater Montréal (Canada) area.

Underflow baffles have gained in popularity over the years as a viable mean to intercept floatables in Combined Sewer Overflows (CSOs). This choice was mainly justified by the extremely low capital cost (CAPEX) and operational cost (OPEX) of this solution, although the efficiency of underflow baffles has never been clearly proven. The only similar application to underflow baffles are scum boards in grit chambers and clarifier. However, the flow conditions at CSOs vary considerably from those in grit chambers and clarifier. For this reason, review of the behavior of floatables in a rapid flow is paramount. Only then can comprehensive design criteria for underflow baffles and overflow chambers be suggested. Pilot scale tests, performed in a 17 metres long basin at various flowrates, had already shown that a critical horizontal velocity for floatables (Vcr) may develop in the overflow chambers. In this follow up study, the fate of intercepted floatables was investigated. It appears from this latest data that permanent capture of floatables decreases rapidly with an increase in the horizontal velocity of the flow, no matter what the baffle depth. Baffle depth increases capture at lower velocities (0.17 m/s) but become irrelevant at higher velocities (0.61 m/s). This data suggests that capture efficiency of existing underflow baffles in overflow chambers can be, at best, very low whenever the horizontal velocity increases above 0.30 m/s or 1 ft/s.     

Identification of microstructural zones and thermal cycles in a weldment of modified 9Cr-1Mo steel

This paper presents the results of a study on the microstructural and microchemical variations in a multipass Gas Tungsten Arc weld (GTAW) of modified 9Cr-1Mo steel. The changes brought about in the steel due to the heating and cooling cycles during welding and the subsequent effects due to reheating effects during multipass welding are described. Detailed analytical transmission electron microscopy has been carried to study the type and composition of the primary and secondary phases in this steel. The systematic changes in microstructural parameters such as Prior Austenite Grain Size, martensite lath size, number density, size and microchemistry of carbides, have been understood based on the different transformations that the steel undergoes during the heating and cooling process. Based on the observed microstructure, an attempt has been made to identify distinct microstructural zones and possible thermal cycles experienced by different regions of the weldment.     

Optimized hydrogen positions for aluminium and iron containing hydroxide minerals

The structures of a number of hydroxide and oxyhydroxide minerals have previously been reported without the hydrogen positions explicitly defined. Here we use two atomic scale computer simulation techniques, one based on classical ionic potentials, the other on density functional theory (DFT), to predict these positions. The aim is not only to provide data that can be used as the basis for future experimental structure optimizations but also model parameters that can be used to predict complex hydroxide structures. The efficacy of the approach is demonstrated through the comparison of predicted and experimental data for minerals whose hydrogen positions are known.