Time-domain-finite-wave analysis of the engine exhaust system by means of the stationary-frame method of characteristics. Part I. Theory

Time-domain-finite-wave analysis of the engine exhaust system is usually done using the method of characteristics. This makes use of either the moving frame method, or the stationary frame method. The stationary frame method is more convenient than its counterpart inasmuch as it avoids the tedium of graphical computations. In this paper (part I), the stationary-frame computational scheme along with the boundary conditions has been implemented. The analysis of a uniform tube, cavity-pipe junction including the engine and the radiation ends, and also the simple area discontinuities has been presented. The analysis has been done accounting for wall friction and heat-transfer for a one-dimensional unsteady flow. In the process, a few inconsistencies in the formulations reported in the literature have been pointed out and corrected. In the accompanying paper (part II) results obtained from the simulation are shown to be in good agreement with the experimental observations.

Influence of grain size on high temperature fracture in a Mg AZ31 alloy

Tensile experiments at 673 K and grain sizes from similar to 8 to 17 mu m revealed large ductility at a low strain rate and a reduced ductility at a high strain rate, corresponding to a change from a high to a low value for the strain rate sensitivity. High strain rate deformation led to fracture by flow localization, whereas low strain rate deformation involved fracture by cavity nucleation and growth. Analysis revealed that grain boundary migration can assist significantly in reducing the stress concentrations caused by grain boundary sliding, thereby retarding cavity nucleation. Calculations demonstrate that the interlinkage of voids parallel and perpendicular to the tensile axis occurs significantly, so that it is not always possible to use the cavity shapes to distinguish between diffusion and plasticity controlled growth. Cavitation damage evolves slowly in materials with a coarser grain size because of reduced nucleation related to a reduction in the strain rate sensitivity and associated grain boundary sliding. (C) 2011 Elsevier B.V. All rights reserved.

Modelling of a batch sonochemical reactor

Ultrasonication of aqueous KI solution is known to yield I2 due to reaction of iodide ions with hydroxyl radicals, which in turn are generated due to cavitation. Based on this conceptual framework, a model has been developed to predict the rate of iodine formation for KI solutions of various concentrations under different gas atmospheres. The model follows the growth and collapse of a gas—vapour cavity using the Rayleigh—Plesset bubble dynamics equation. The bubble is assumed to behave isothermally during its growth phase and a part of the collapse phase. Thereafter it is assumed to collapse adiabatically, yielding high temperatures and pressures. Thermodynamic equilibrium is assumed in the bubble at the end of collapse phase. The contents of the bubble are assumed to mix with the liquid, and the reactor contents are assumed to be well stirred. The model has been verified by conducting experiments with KI solutions of different concentrations and using different gas atmospheres. The model not only explains these results but also the existence of a maximum when Ar---O2 mixtures of different compositions are employed.

Modelling of a batch sonochemical reactor

Ultrasonication of aqueous KI solution is known to yield I2 due to reaction of iodide ions with hydroxyl radicals, which in turn are generated due to cavitation. Based on this conceptual framework, a model has been developed to predict the rate of iodine formation for KI solutions of various concentrations under different gas atmospheres. The model follows the growth and collapse of a gas-vapour cavity using the Rayleigh-Plesset bubble dynamics equation. The bubble is assumed to behave isothermally during its growth phase and a part of the collapse phase. Thereafter it is assumed to collapse adiabatically, yielding high temperatures and pressures. Thermodynamic equilibrium is assumed in the bubble at the end of collapse phase. The contents of the bubble are assumed to mix with the liquid, and the reactor contents are assumed to be well stirred. The model has been verified by conducting experiments with KI solutions of different concentrations and using different gas atmospheres. The model not only explains these results but also the existence of a maximum when Ar-O2 mixtures of different compositions are employed.

Sorbate properties of xenon in cloverite: A molecular dynamics study

Molecular dynamics calculations on xenon adsorbed in the cubic cavity of cloverite, a gallophosphate, is presented. Guest-host radial distribution functions, guest-host energy distribution functions, power spectra, and diffusion coefficients for xenon are reported at 397, 494, and 716 K. Results suggest that xenon is highly mobile at 700 K. A shift in the peak position of the power spectra toward lower frequency is observed with increase in temperature. (C) 1994 Academic Press, Inc.

The Reaction of a Nitro-Capped Cobalt(III) Cage Complex With Base: the Crystal Structure of a Contracted Cage Complex, and the Mechanism of Its Formation

The synthesis, properties and crystal structure of the cage complex (1-hydroxy-8-methyl-3,6,10,13,15,18-hexaazabicyclo[6.6.5]nonadecane)cobalt(III) chloride hydrate ([Co(Me,OH-absar)] C13.H2O) are reported. The mechanism of the formation of this contracted cavity cage from a nitro-capped hexaazabicycloicosane type cage has been investigated. Treatment of (1-methyl-8-nitro-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane)cobalt(III) chloride ([Co(Me,NO2-sar)] 3+) with excess base in aqueous solution leads initially to rapid (t1/2 < 1 ms) and reversible deprotonation of one coordinated secondary amine. This species undergoes a retro-Mannich type reaction and imine hydrolysis (t1/2 almost-equal-to 90 s). Quenching the reaction with acid gives rise to a pair of isomeric intermediate species which have been isolated and characterized. They have a pendant arm macrocyclic structure, resulting from the loss of a methylene unit from one of the arms of the cap. Heating either isomer in aqueous solution gives the new cage compound with the contracted cap. It is postulated that this occurs through a Nef reaction, resulting in the formation of a ketone which then condenses with the coordinated primary amine. A comparison with the corresponding bicycloicosane analogue indicates a reduced chromophoric cavity size for the contracted cage. The reduction potential of the cobalt(III)/cobalt(II) couple is 170 mV more negative for the smaller cage, and, in the electronic spectrum of the cobalt(III) complex, the d-d transitions are both shifted to higher energy, corresponding to a stronger ligand field.

Thermodynamic and structural consequences of changing a sulfur atom to a methylene group in the M13Nle mutation in ribonuclease-S

Two fragments of pancreatic ribonuclease A, a truncated version of S-peptide (residues 1-15) and S-protein (residues 21-124), combine to give a catalytically active complex. We have substituted the wild-type residue at position 13, methionine (Met), with norleucine (Nle), where the only covalent change is the replacement of the sulfur atom with a methylene group. The thermodynamic parameters associated with the binding of this variant to S-protein, determined by titration calorimetry in the temperature range 10-40 degrees C, are reported and compared to values previously reported [Varadarajan, R., Connelly, P. R., Sturtevant, J. M., & Richards, F. M. (1992) Biochemistry 31, 1421-1426] for other position 13 analogs. The differences in the free energy and enthalpy of binding between the Met and Nle peptides are 0.6 and 7.9 kcal/mol at 25 degrees C, respectively. These differences are slightly larger than, but comparable to, the differences in the values for the Met/Ile and Met/Leu pairs. The structure of the mutant complex was determined to 1.85 Angstrom resolution and refined to an R-factor of 17.4% The structures of mutant and wild-type complexes are practically identical although the Nle side chain has a significantly higher average B-factor than the corresponding Met side chain. In contrast, the B-factors of the atoms of the cage of residues surrounding position 13 are all somewhat lower in the Nle variant than in the Met wild-type. Thus, the large differences in the binding enthalpy appear to reside entirely in the difference in chemical properties or dynamic behavior of the -S- and -CH2- groups and not in differences in the geometry of the side chains or the internal cavity surface. In addition, a novel method of obtaining protein stability data by means of isothermal titration calorimetry is introduced.

Application of scaled particle theory to alkyl-aryl surfactants: a two zone model of micellar core

Scaled Particle Theory (SPT) has been applied to predict the total free energies of micellization of ionic as well as nonionic micellar systems containing an aryl ring. A modification of the previously developed model has been made, proposing a two-zone model of micellar core which corroborates with the structural information available for such systems. The results are in good agreement with experimental data and also confirm the dictating role of cavity forming free energies for such systems