Reactions of cyanogen radical with alkanes and an explanation for negative temperature dependence of rate constants

Reactions of cyanide radicals with alkanes have been investigated by ab initio methods. It is found that the potential energy surface for reaction of CN with a primary C-H bond in methane has a small positive barrier while reactions of CN with a secondary and a tertiary C-H bond in alkanes are barrierless at the correlated level. A simple explanation for the obtained negative temperature dependence of rate constants for reactions of CN with a secondary and a tertiary C-H bond in alkanes are given in terms of the collision theory of bimolecular reactions. It is shown that for barrierless reactions the negative temperature dependence of the rate constants is attributed to the variation of the pre-exponential factor with temperature.

Multifunctional cryogenic sensors from n-BaTiO3 ceramics having strong negative temperature coefficient of resistance

Donor-doped n-BaTiO3 polycrystalline ceramics show a strong negative temperature coefficient of resistivity below the orthorhombic-rhombohedral phase transition point, from 10(2-3) Omega cm af 190 K to 10(10-13) Omega cm at less than or similar to 50 K, with thermal coefficient of resistance alpha = 20-23% K-1. Stable thermal sensors for low-temperature applications are realized therefrom. The negative temperature coefficient of resistivity region can be modified by substituting isovalent ions in the lattice. Highly nonlinear current-voltage (I-V) curves are observed at low temperatures, with a voltage maximum followed by the negative differential resistance. The I-V curves are sensitive to dissipation so that cryogenic sensors can be fabricated for liquid level control, flow rate monitoring, radiation detection or in-rush voltage limitation.

Effect of Constant and Cyclic Current Stressing on the Evolution of Intermetallic Compound Layers

In this paper the effects of constant and cyclic power loads on the evolution of interfacial reaction layers in lead-free solder interconnections are presented. Firstly, the differences in the growth behavior of intermetallic compound (IMC) layers at the cathode and anode sides of the interconnections are rationalized. This is done by considering the changes in the intrinsic fluxes of elements owing to electromigration as well as taking into account the fact that the growth of Cu3Sn and Cu6Sn5 are coupled via interfacial reactions. In this way, better understanding of the effect of electron flux on the growth of each individual layer in the Cu-Sn system can be achieved. Secondly, it is shown that there is a distinct difference between steady-state current stressing (constant current, constant temperature) and power cycling with alternating on- and off-cycle periods (accompanied by a change of temperature). The reasons behind the observed differences are subsequently discussed. Finally, special care is taken to ensure that the current densities are chosen in such a way that there is no risk for even partial melting of the solder interconnections.

Nonlinear dynamics and chaotic motions in feedback-controlled two- and three-degree-of-freedom robots

The dynamics of a feedback-controlled rigid robot is most commonly described by a set of nonlinear ordinary differential equations. In this paper we analyze these equations, representing the feedback-controlled motion of two- and three-degrees-of-freedom rigid robots with revolute (R) and prismatic (P) joints in the absence of compliance, friction, and potential energy, for the possibility of chaotic motions. We first study the unforced or inertial motions of the robots, and show that when the Gaussian or Riemannian curvature of the configuration space of a robot is negative, the robot equations can exhibit chaos. If the curvature is zero or positive, then the robot equations cannot exhibit chaos. We show that among the two-degrees-of-freedom robots, the PP and the PR robot have zero Gaussian curvature while the RP and RR robots have negative Gaussian curvatures. For the three-degrees-of-freedom robots, we analyze the two well-known RRP and RRR configurations of the Stanford arm and the PUMA manipulator respectively, and derive the conditions for negative curvature and possible chaotic motions. The criteria of negative curvature cannot be used for the forced or feedback-controlled motions. For the forced motion, we resort to the well-known numerical techniques and compute chaos maps, Poincare maps, and bifurcation diagrams. Numerical results are presented for the two-degrees-of-freedom RP and RR robots, and we show that these robot equations can exhibit chaos for low controller gains and for large underestimated models. From the bifurcation diagrams, the route to chaos appears to be through period doubling.

A current error space vector based hysteresis controller with constant switching frequency and simple online boundary computation for VSI fed IM drive

This paper proposes a simple current error space vector based hysteresis controller for two-level inverter fed Induction Motor (IM) drives. This proposed hysteresis controller retains all advantages of conventional current error space vector based hysteresis controllers like fast dynamic response, simple to implement, adjacent voltage vector switching etc. The additional advantage of this proposed hysteresis controller is that it gives a phase voltage frequency spectrum exactly similar to that of a constant switching frequency space vector pulse width modulated (SVPWM) inverter. In this proposed hysteresis controller the boundary is computed online using estimated stator voltages along alpha and beta axes thus completely eliminating look up tables used for obtaining parabolic hysteresis boundary proposed in. The estimation of stator voltage is carried out using current errors along alpha and beta axes and steady state model of induction motor. The proposed scheme is simple and capable of taking inverter upto six step mode operation, if demanded by drive system. The proposed hysteresis controller based inverter fed drive scheme is simulated extensively using SIMULINK toolbox of MATLAB for steady state and transient performance. The experimental verification for steady state performance of the proposed scheme is carried out on a 3.7kW IM.

Constant pressure laminar, transitional and turbulent flows - An approximate unified treatment

A nondimensional number that is constant in two-dimensional, incompressible and constant pressure laminar and fully turbulent boundary, layer flows has been proposed. An extension of this to constant pressure transitional flow is discussed.

Tracking and erosion resistance of silicone rubber nanocomposites under positive and negative dc voltages

ASTM D2303 standard provides a method for evaluating the tracking and erosion resistance of polymeric insulators under ac voltages. In this paper, the above method has been extended for evaluating the performance of the insulators under dc stresses. Tests were conducted on polymeric silicone rubber (SR) insulators under positive and negative dc stresses. Micron sized Alumina trihydrate (uATH) and nano sized Alumina (nALU) were used as fillers in SR matrix to improve the resistance to tracking and erosion. Results suggest that SR composites perform better under negative dc than under positive dc voltages. Eroded mass and leakage current data support the above result. Samples with low concentration of nano alumina fillers performed on par with the samples with large loadings of uATH.

Seismic passive resistance in soils for negative wall friction

: In the presence of pseudo-static seismic forces, passive earth pressure coefficients behind retaining walls were generated using the limit equilibrium method of analysis for the negative wall friction angle case (i.e., the wall moves upwards relative to the backfill) with logarithmic spirals as rupture surfaces. Individual density, surcharge, and cohesion components were computed to obtain the total minimum seismic passive resistance in soils by adding together the individual minimum components. The effect of variation in wall batter angle, ground slope, wall friction angle, soil friction angle, and horizontal and vertical seismic accelerations on seismic passive earth pressures are considered in the analysis. The seismic passive earth pressure coefficients are found to be highly sensitive to the seismic acceleration coefficients both in the horizontal and the vertical directions. The results are presented in graphical and tabular formats.

Curvature of the vapour pressure curve

This paper brings out the existence of the maximum in the curvature of the vapour pressure curve. It occurs in the reduced temperature range of 0.6–0.7 for all liquids and has a value of 3.8–4.8. A set of 17 working fluids consisting of several refrigerants, carbon dioxide, cryogenic liquids and water are taken as test fluids. There exists also a minimum close to the critical point which can be observed only when a thermodynamically consistent functional form of the vapour pressure equation is chosen. This feature, in addition to throwing some light on the behaviour of the vapour pressure curve, could provide some useful inputs to the choice of working fluids for vapour pressure thermometers and thermostatic expansion valves.

Surfaces of Bounded Mean Curvature In Riemannian Manifolds

Consider a sequence of closed, orientable surfaces of fixed genus g in a Riemannian manifold M with uniform upper bounds on the norm of mean curvature and area. We show that on passing to a subsequence, we can choose parametrisations of the surfaces by inclusion maps from a fixed surface of the same genus so that the distance functions corresponding to the pullback metrics converge to a pseudo-metric and the inclusion maps converge to a Lipschitz map. We show further that the limiting pseudo-metric has fractal dimension two. As a corollary, we obtain a purely geometric result. Namely, we show that bounds on the mean curvature, area and genus of a surface F subset of M, together with bounds on the geometry of M, give an upper bound on the diameter of F. Our proof is modelled on Gromov's compactness theorem for J-holomorphic curves.

Effect of longitudinal surface curvature on boundary layers

We consider here the higher order effect of moderate longitudinal surface curvature on steady, two-dimensional, incompressible laminar boundary layers. The basic partial differential equations for the problem, derived by the method of matched asymptotic expansions, are found to possess similarity solutions for a family of surface curvatures and pressure gradients. The similarity equations obtained by this anaylsis have been solved numerically on a computer, and show a definite decrease in skin friction when the surface has convex curvature in all cases including zero pressure gradient. Typical velocity profiles and some relevant boundary-layer characteristics are tabulated, and a critical comparison with previous work is given.

Axisymmetric turbulent boundary layer along a circular cylinder at constant pressure

A constant-pressure axisymmetric turbulent boundary layer along a circular cylinder of radius a is studied at large values of the frictional Reynolds number a+ (based upon a) with the boundary-layer thickness δ of order a. Using the equations of mean motion and the method of matched asymptotic expansions, it is shown that the flow can be described by the same two limit processes (inner and outer) as are used in two-dimensional flow. The condition that the two expansions match requires the existence, at the lowest order, of a log region in the usual two-dimensional co-ordinates (u+, y+). Examination of available experimental data shows that substantial log regions do in fact exist but that the intercept is possibly not a universal constant. Similarly, the solution in the outer layer leads to a defect law of the same form as in two-dimensional flow; experiment shows that the intercept in the defect law depends on δ/a. It is concluded that, except in those extreme situations where a+ is small (in which case the boundary layer may not anyway be in a fully developed turbulent state), the simplest analysis of axisymmetric flow will be to use the two-dimensional laws with parameters that now depend on a+ or δ/a as appropriate.

Shear banding in a yield stress bearing Langmuir monolayer

We examine the shear-thinning behaviour of a two dimensional yield stress bearing monolayer of sorbitan tristearate at air/water interface. The flow curve consists of a linear region at low shear stresses/shear rates, followed by a stress plateau at higher values. The velocity profile obtained from particle imaging velocimetry indicates that shear banding occurs, showing coexistence of the fluidized region near the rotor and solid region with vanishing shear-rate away from the rotor. In the fluidized region, the velocity profile, which is linear at low shear rates, becomes exponential at the onset of shear-thinning, followed by a time varying velocity profile in the plateau region. At low values of constant applied shear rates, the viscosity of the film increases with time, thus showing aging behaviour like in soft glassy three-dimensional (3D) systems. Further, at the low values of the applied stress in the yield stress regime, the shear-rate fluctuations in time show both positive and negative values, similar to that observed in sheared 3D jammed systems. By carrying out a statistical analysis of these shear-rate fluctuations, we estimate the effective temperature of the soft glassy monolayer using the Galavatti-Cohen steady state fluctuation relation.