Effect of welding process on fatigue crack growth behaviour of austenitic stainless steel welds in a low alloy (Q & T) steel

Fatigue crack growth behaviour from a lack of penetration (LOP) defect in austenitic stainless steel weld metals of cruciform joints made of a low alloy high strength (Q & T) steel has been studied to understand the effect of two welding processes, namely, shielded metal arc welding (SMAW) and flux cored arc welding (FCAW). Fatigue crack growth studies were carried out at a stress ratio of R = 0 and a frequency of 90 to 110 Hz in a resonant testing equipment (Rumul, Model:8601). Crack growth rates were relatively lower in the weld metal obtained by flux cored arc welding process. Microstructural features observed revealed marked difference in the morphology of delta ferrite for the welded joints obtained from the above two welding processes. Long streaks of delta ferrite in austenite matrix were found in case of SMAW-weld metal which seem to have lowered the resistance to the fatigue crack propagation. A discontinuous network of delta ferrite found in austenite matrix in the case of FCAW-weld metal seems to have contributed to slower propagation of fatigue crack. Fractographic features also substantiate the observed trends in the fatigue crack growth behaviour.     

Dissipative Cylindrical Collapse of Charged Anisotropic Fluid

We have studied the dynamics of a cylindrical column of anisotropic, charged fluid which is experiencing dissipation in the form of heat flow, free-streaming radiation, and shearing viscosity, undergoing gravitational collapse. We calculate the Einstein-Maxwell field equations and, using the Darmois junction conditions, match the interior non-static cylindrically symmetric space-time with the exterior anisotropic, charged, cylindrically symmetric space-time. The behavior of the density, pressure and luminosity of the collapsing matter has been analyzed. From the dynamical equations, the effect of charge and dissipative quantities over the cylindrical collapse are studied. Finally, we have derived the solutions for the collapsing matter which is valid during the later stages of collapse and have discussed the significance from a physical standpoint.     

N,N-bis-(2-benzimidazolylmethyl)L-methionine: An efficient Ag(I) extractant

A new ligand N,N-bis-(2-benzimidazolylmethyl)L-methionine has been synthesized and well characterized by different analytical techniques. The ligand has a very strong affinity for silver(I) and is used for the selective extraction of silver ions from aqueous solution into 1-butanol. The effect of concentration of Ag(I), pH, diverse ions, and temperature on the extraction is reported. The developed method has success-fully been applied to the determination of silver in different samples. Radiotracer technique, using ^110mAg(I) as a tracer, has been used for monitoring the concentration of silver ion.     

Experimental investigation on the mechanism of chelation-assisted, copper(II) acetate-accelerated azide-alkyne cycloaddition

A mechanistic model is formulated to account for the high reactivity of chelating azides (organic azides capable of chelation-assisted metal coordination at the alkylated azido nitrogen position) and copper(II) acetate (Cu(OAc)(2)) in copper(II)-mediated azide-alkyne cycloaddition (AAC) reactions. Fluorescence and (1)H NMR assays are developed for monitoring the reaction progress in two different solvents, methanol and acetonitrile. Solvent kinetic isotopic effect and premixing experiments give credence to the proposed different induction reactions for converting copper(II) to catalytic copper(I) species in methanol (methanol oxidation) and acetonitrile (alkyne oxidative homocoupling), respectively. The kinetic orders of individual components in a chelation-assisted, copper(II)-accelerated AAC reaction are determined in both methanol and acetonitrile. Key conclusions resulting from the kinetic studies include (1) the interaction between copper ion (either in +1 or +2 oxidation state) and a chelating azide occurs in a fast, pre-equilibrium step prior to the formation of the in-cycle copper(I)-acetylide, (2) alkyne deprotonation is involved in several kinetically significant steps, and (3) consistent with prior experimental and computational results by other groups, two copper centers are involved in the catalysis. The X-ray crystal structures of chelating azides with Cu(OAc)(2) suggest a mechanistic synergy between alkyne oxidative homocoupling and copper(II)-accelerated AAC reactions, in which both a bimetallic catalytic pathway and a base are involved. The different roles of the two copper centers (a Lewis acid to enhance the electrophilicity of the azido group and a two-electron reducing agent in oxidative metallacycle formation, respectively) in the proposed catalytic cycle suggest that a mixed valency (+2 and +1) dinuclear copper species be a highly efficient catalyst. This proposition is supported by the higher activity of the partially reduced Cu(OAc)(2) in mediating a 2-picolylazide-involved AAC reaction than the fully reduced Cu(OAc)(2). Finally, the discontinuous kinetic behavior that has been observed by us and others in copper(I/II)-mediated AAC reactions is explained by the likely catalyst disintegration during the course of a relatively slow reaction. Complementing the prior mechanistic conclusions drawn by other investigators, which primarily focus on the copper(I)/alkyne interactions, we emphasize the kinetic significance of copper(I/II)/azide interaction. This work not only provides a mechanism accounting for the fast Cu(OAc)(2)-mediated AAC reactions involving chelating azides, which has apparent practical implications, but suggests the significance of mixed-valency dinuclear copper species in catalytic reactions where two copper centers carry different functions.     

Revisiting the reactivity of different carbon bases: A theoretical study

Quantum chemical calculations are performed on different carbon bases to understand the origin of their reactivity. Both carbon(0) and carbon(II) bases may show very high values of second proton affinity as well as bond dissociation energies for gem‐dimetallation. Thus, their distinction becomes blurred when subjected to electrophilic attack. However, unlike carbon(0) bases, carbon(II) bases are ambiphilic in nature owing to the presence of a σ symmetric lone pair and a vacant π orbital concentrated on the central carbon atom. Thus, they may show different reactivity when subjected to nucleophilic attack. This reactivity difference may be considered as another distinction between these two classes of compounds. © 2013 Wiley Periodicals, Inc.     

Metriplectic structure, Leibniz dynamics and dissipative systems

A metriplectic (or Leibniz) structure on a smooth manifold is a pair of skew-symmetric Poisson tensor P and symmetric metric tensor G. The dynamical system defined by the metriplectic structure can be expressed in terms of Leibniz bracket. This structure is used to model the geometry of the dissipative systems. The dynamics of purely dissipative systems are defined by the geometry induced on a phase space via a metric tensor. The notion of Leibniz brackets is extendable to infinite-dimensional spaces. We study metriplectic structure compatible with the Euler-Poincaré framework of the Burgers and Whitham-Burgers equations. This means metriplectic structure can be constructed via Euler-Poincaré formalism. We also study the Euler-Poincaré frame work of the Holm-Staley equation, and this exhibits different type of metriplectic structure. Finally we study the 2D Navier-Stokes using metriplectic techniques.     

WKB approximation in complex time

The WKB approximation to the one particle Schrödinger equation in time is used to obtain the wavefunction at a given point as a sum of semiclassical terms, each corresponding to a different classical trajectory (real or complex) but ending up at the same point. A method to find out reflection coefficient for processes involving one and two turning points is developed and it is shown that the semiclassical complex analysis reproduces exactly the reflection coefficient that is obtained through the exact solution of the problem. The connection between pair production and reflection amplitude is also shown. The pair production amplitude in a time dependent gravitational background is calculated and it is shown that the vacuum considered in complex trajectory WKB analysis refers to adiabatic vacuum.     

Particle Motion and Perturbed Dynamical System in Warped Product Spacetimes

In this paper we have used the dynamical systems analysis to study the dynamics of a five-dimensional universe in the form of a warped product spacetime with a spacelike dynamic extra dimension. We have decomposed the geodesic equations to get the motion along the extra dimension and have studied the associated dynamical system when the cross-diagonal element of the Einstein tensor vanishes, and also when it is non-vanishing. Introducing the concept of an energy function along the phase path in terms of the extra-dimensional coordinate, we have examined how the energy function depends on the warp factor. The energy function serves as a measure of the amount of perturbation of geodesic paths along the extra dimension in the region close to the brane. Then we studied the geodesic motion under a conventional metric perturbation in the form of homothetic motion and conformal motion and examined the nature of critical points for a Mashhoon-Wesson-type metric, for timelike and null geodesics when the cross-diagonal term of the Einstein tensor vanishes. Finally we investigated the motion for null and timelike geodesics under the condition when the cross-diagonal element of the Einstein tensor is non-vanishing and examined the effects of perturbation on the critical points of the dynamical system.