Potential-distance relationships of clay-water systems considering the Stern theory

This paper deals with the use of Stem theory as applied to a clay-water electrolyte system, which is more realistic to understand the force system at micro level man the Gouy-Chapman theory. The influence of the Stern layer on potential-distance relationship has been presented quantitatively for certain specified clay-water systems and the results are compared with the Gouy-Chapman model. A detailed parametric study concerning the number of adsorption spots on the clay platelet, the thickness of the Stern layer, specific adsorption potential and the value of dielectric constant of the pore fluid in the Stern layer, was carried out. This study investigates that the potential obtained at any distance using the Stern theory is higher than that obtained by the Gouy-Chapman theory. The hydrated size of the ion is found to have a significant influence on the potential-distance relationship for a given clay, pore fluid characteristics and valence of the exchangeable ion.

Tunable Brownian vortex at the interface

A general kind of Brownian vortices is demonstrated by applying an external nonconservative force field to a colloidal particle bound by a conservative optical trapping force at a liquid-air interface. As the liquid medium is translated at a constant velocity with the bead trapped at the interface, the drag force near the surface provides enough rotational component to bias the particle's thermal fluctuations in a circulatory motion. The interplay between the thermal fluctuations and the advection of the bead in constituting the vortex motions is studied, and we infer that the angular velocity of the circulatory motion offers a comparative measure of the interface fluctuations.

The stretching of single poly-ubiquitin molecules: Static versus dynamic disorder in the non-exponential kinetics of chain unfolding

Static disorder has recently been implicated in the non-exponential kinetics of the unfolding of single molecules of poly-ubiquitin under a constant force Kuo, Garcia-Manyes, Li, Barel, Lu, Berne, Urbakh, Klafter, and Fernandez, Proc. Natl. Acad. Sci. U. S. A. 107, 11336 (2010)]. In the present paper, it is suggested that dynamic disorder may provide a plausible, alternative description of the experimental observations. This suggestion is made on the basis of a model in which the barrier to chain unfolding is assumed to be modulated by a control parameter r that evolves in a parabolic potential under the action of fractional Gaussian noise according to a generalized Langevin equation. The treatment of dynamic disorder within this model is pursued using Zwanzig's indirect approach to noise averaging Acc. Chem. Res. 23, 148 (1990)]. In conjunction with a self-consistent closure scheme developed by Wilemski and Fixman J. Chem. Phys. 58, 4009 (1973); ibid. 60, 866 (1974)], this approach eventually leads to an expression for the chain unfolding probability that can be made to fit the corresponding experimental data very closely. (C) 2011 American Institute of Physics.

SCF and electron correlation studies on structure, force constants and vibrational spectra of borane monoammoniate complex

Effects of basis set and electron correlation on the equilibrium geometry, force constants and vibrational spectra of BH3NH3 have been studied. A series of basis sets ranging from double zeta to triple zeta including polarization and diffuse functions have been utilized. All the SCF based calculations overestimate the dative B-N bond distance and considerable improvement occurs when the treatment for electron correlation is introduced. Detailed vibrational analysis for BH3NH3 has been carried out. The mean absolute percentage deviation of the ab initio predicted vibration frequencies of (BH3NH3)-B-11 from the experiment is about 10% for the SCF based calculations and the MP2 method shows better agreement, the overall deviation being 5-6%. The ground state effective force constants of BH3NH3 were obtained using RECOVES procedure. The RECOVES sets of force constants are found to be highly satisfactory for the prediction of the vibrational frequencies of different isotopomers of BH3NH3. The mean absolute percentage deviation of the calculated frequencies of different isotopomers from the experiment is much less than 1%. The RECOVES-MP2/augDZP set of force constants was found to be the best set among the different sets for this molecule. Theoretical infrared intensities are in fair agreement with the observed spectral features.

Theoretical Analysis of the Electromotive Force of a Cell Incorporating a Composition Gradient Solid Electrolyte

New composition gradient solid electrolytes have been designed for application in high temperature solid-state galvanic sensors and in thermodynamic measurements. The functionally gradient electrolyte consists of a solid solution between two or more ionic conductors with a common ion and gradual variation in composition of the other ionic species. Unequal rates of migration of the ions, caused by the presence of the concentration gradient, may result in the development of space charge, manifesting as diffusion potential. Presented is a theoretical analysis of the EMF of cells incorporating gradient solid electrolytes. An analytical expression is derived for diffusion potential, using the thermodynamics of irreversible processes, for different types of concentration gradients and boundary conditions at the electrode/electrolyte interfaces. The diffusion potential of an isothermal cell incorporating these gradient electrolytes becomes negligible if there is only one mobile ion and the transport numbers of the relatively immobile polyionic species and electrons approach zero. The analysis of the EMF of a nonisothermal cell incorporating a composition gradient solid electrolyte indicates that the cell EMF can be expressed in terms of the thermodynamic parameters at the electrodes and the Seebeck coefficient of the gradient electrolyte under standard conditions when the transport number of one of the ions approaches unity.

Vibration Signature Analysis Using Artificial Neural Networks

Damage detection by measuring and analyzing vibration signals in a machine component is an established procedure in mechanical and aerospace engineering. This paper presents vibration signature analysis of steel bridge structures in a nonconventional way using artificial neural networks (ANN). Multilayer perceptrons have been adopted using the back-propagation algorithm for network training. The training patterns in terms of vibration signature are generated analytically for a moving load traveling on a trussed bridge structure at a constant speed to simulate the inspection vehicle. Using the finite-element technique, the moving forces are converted into stationary time-dependent force functions in order to generate vibration signals in the structure and the same is used to train the network. The performance of the trained networks is examined for their capability to detect damage from unknown signatures taken independently at one, three, and five nodes. It has been observed that the prediction using the trained network with single-node signature measurement at a suitability chosen location is even better than that of three-node and five-node measurement data.

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.

Solvation dynamics in monohydroxy alcohols: Agreement between theory and different experiments

Recently three different experimental studies on ultrafast solvation dynamics in monohydroxy straight-chain alcohols (C-1-C-4) have been carried out, with an aim to quantify the time constant (and the amplitude) of the ultrafast component. The results reported are, however, rather different from different experiments. In order to understand the reason for these differences, we have carried out a detailed theoretical study to investigate the time dependent progress of solvation of both an ionic and a dipolar solute probe in these alcohols. For methanol, the agreement between the theoretical predictions and the experimental results [Bingemann and Ernsting J. Chem. Phys. 1995, 102, 2691 and Horng et al. J: Phys, Chern, 1995, 99, 17311] is excellent. For ethanol, propanol, and butanol, we find no ultrafast component of the time constant of 70 fs or so. For these three liquids, the theoretical results are in almost complete agreement with the experimental results of Horng et al. For ethanol and propanol, the theoretical prediction for ionic solvation is not significantly different from that of dipolar solvation. Thus, the theory suggests that the experiments of Bingemann and Ernsting and those of Horng et al. studied essentially the polar solvation dynamics. The theoretical studies also suggest that the experimental investigations of Joo et al. which report a much faster and larger ultrafast component in the same series of solvents (J. Chem. Phys. 1996, 104, 6089) might have been more sensitive to the nonpolar part of solvation dynamics than the polar part. In addition, a discussion on the validity of the present theoretical approach is presented. In this theory the ultrafast component arises from almost frictionless inertial motion of the individual solvent molecules in the force field of its neighbors.

Micromechanical modeling of granular materials: effect of confining pressure on mechanical behavior

This paper reports the effect of confining pressure on the mechanical behavior of granular materials from micromechanical considerations starting from the grain scale level, based on the results of numerically simulated tests on disc assemblages using discrete element modeling (DEM). The two macro parameters which are influenced by the increase in confining pressure are stiffness (increases) and volume change (decreases). The lateral strain coefficient (Poisson's ratio) at the beginning of the test is more or less constant. The angle of internal friction slightly decreases with increase in confining pressure. The numerical results of disc assemblages indicate very clearly a non-linear Mohr-Coulomb failure envelope with increase in confining pressure. The increase in average coordination number and accompanying decrease of fabric anisotropy reduce the shear strength at higher confining pressures. Micromechanical explanations of the macroscopic behavior are presented in terms of the force and fabric anisotropy coefficients. (C) 1999 Elsevier Science Ltd. AII rights reserved.

Velocity distribution for a dilute vibrated granular material

The velocity distribution for a vibrated granular material is determined in the dilute limit where the frequency of particle collisions with the vibrating surface is large compared to the frequency of binary collisions. The particle motion is driven by the source of energy due to particle collisions with the vibrating surface, and two dissipation mechanisms-inelastic collisions and air drag-are considered. In the latter case, a general form for the drag force is assumed. First, the distribution function for the vertical velocity for a single particle colliding with a vibrating surface is determined in the limit where the dissipation during a collision due to inelasticity or between successive collisions due to drag is small compared to the energy of a particle. In addition, two types of amplitude functions for the velocity of the surface, symmetric and asymmetric about zero velocity, are considered. In all cases, differential equations for the distribution of velocities at the vibrating surface are obtained using a flux balance condition in velocity space, and these are solved to determine the distribution function. It is found that the distribution function is a Gaussian distribution when the dissipation is due to inelastic collisions and the amplitude function is symmetric, and the mean square velocity scales as [[U-2](s)/(1 - e(2))], where [U-2](s) is the mean square velocity of the vibrating surface and e is the coefficient of restitution. The distribution function is very different from a Gaussian when the dissipation is due to air drag and the amplitude function is symmetric, and the mean square velocity scales as ([U-2](s)g/mu(m))(1/(m+2)) when the acceleration due to the fluid drag is -mu(m)u(y)\u(y)\(m-1), where g is the acceleration due to gravity. For an asymmetric amplitude function, the distribution function at the vibrating surface is found to be sharply peaked around [+/-2[U](s)/(1-e)] when the dissipation is due to inelastic collisions, and around +/-[(m +2)[U](s)g/mu(m)](1/(m+1)) when the dissipation is due to fluid drag, where [U](s) is the mean velocity of the surface. The distribution functions are compared with numerical simulations of a particle colliding with a vibrating surface, and excellent agreement is found with no adjustable parameters. The distribution function for a two-dimensional vibrated granular material that includes the first effect of binary collisions is determined for the system with dissipation due to inelastic collisions and the amplitude function for the velocity of the vibrating surface is symmetric in the limit delta(I)=(2nr)/(1 - e)much less than 1. Here, n is the number of particles per unit width and r is the particle radius. In this Limit, an asymptotic analysis is used about the Limit where there are no binary collisions. It is found that the distribution function has a power-law divergence proportional to \u(x)\((c delta l-1)) in the limit u(x)-->0, where u(x) is the horizontal velocity. The constant c and the moments of the distribution function are evaluated from the conservation equation in velocity space. It is found that the mean square velocity in the horizontal direction scales as O(delta(I)T), and the nontrivial third moments of the velocity distribution scale as O(delta(I)epsilon(I)T(3/2)) where epsilon(I) = (1 - e)(1/2). Here, T = [2[U2](s)/(1 - e)] is the mean square velocity of the particles.

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.