Structure and Dynamics of Octamethylcyclotetrasiloxane Confined between Mica Surfaces

Using a molecular model for octamethylcydotetrasiloxane (OMCTS), molecular dynamics simulations are carried out to probe the phase state of OMCTS confined between two mica surfaces in equilibrium With a reservoir. Molecular dynamics simulations are carried out for elevations ranging from 5 to 35 K above the melting point for the OMCTS model used in this study. The Helmholtz free energy is, computed for a specific confinement using the :two-phase thermodynamic (2PT) method. Analysis of the in-plane pair correlation functions did not reveal signatures of freezing even under an extreme confinement of two layers. OMCTS is found to orient with a wide distribution of orientations with respect to the mica surface, with a distinct preference for the surface parallel configuration in the contact layers. The self-intermediate scattering function is found to decay with increasing relaxation times as the surface separation is decreased, and the two-step relaxation in the scattering function, a signature of glassy dynamics, distinctly evolves as the temperature is lowered. However, even at 5 K above the melting point, we did not observe a freezing transition and the self-intermediate scattering functions relax within 200 ps for the seven-layered confined system. The self diffusivity and relaxation times obtained from the Kohlrausch-Williams-Watts stretched exponential fits to the late alpha-relaxation exhibit power law scalings with the packing fraction as predicted by mode coupling theory. A distinct discontinuity in the Helmholtz free energy, potential energy, and a sharp change in the local bond order parameter, Q(4), was observed at 230 K for a five-layered system upon cooling, indicative of a first-order transition. A freezing point depression of about 30 K was observed for this five-layered confined system, and at the lower temperatures, contact layers were found to be disordered with long-range order present only in the inner layers. These dynamical signatures indicate that confined OMCTS undergoes a slowdown akin to a fluid approaching a glass transition upon increasing confinement, and freezing under confinement would require substantial subcooling below the bulk melting point of OMCTS.

Fabrication and evaluation of 1 Ah silver/metal hydride cells

Silver/metal hydride (Ag/MH) cells of about 1 Ah capacity have been fabricated and their discharge characteristics at different rates of discharge, faradaic efficiency, cycle life and a.c. impedance have been evaluated. These cells comprise metal-hydride electrodes prepared by employing similar to 60 mu m powder of an AB(2)-Laves phase alloy of nominal composition Zr0.5Ti0.5V0.6Cr0.2Ni1.2 with PTFE binder on a nickel-mesh substrate as the negative plates and commercial-grade silver electrodes as the positive plates. The cells are positive limited and exhibit two distinct voltage plateaus characteristic of two-step reduction of AgO to Ag during their low rates of discharge between C/20 and C/10. This feature is, however, absent when the cells are discharged at C/5 rate. On charging the cells to 100% of their capacity, the faradaic efficiency is found to be 100%. The impedance of the Ag/MH cell is essentially due to the impedance of the silver electrodes, since MH electrodes offer negligible impedance. The cells may be subjected to a large number of charge-discharge cycles with little deterioration.

Mixed Convection Boundary Layer Flow Past a Horizontal Circular Cylinder Embedded in a Bidisperse Porous Medium

Adopting a two-temperature and two-velocity model, appropriate to a bidisperse porous medium (BDPM) proposed by Nield and Kuznetsov (2008), the classical steady, mixed convection boundary layer flow about a horizontal, isothermal circular cylinder embedded in a porous medium has been theoretically studied in this article. It is shown that the boundary layer analysis leads to expressions for the flow and heat transfer characteristics in terms of an inter-phase momentum parameter, a thermal diffusivity ratio, a thermal conductivity ratio, a permeability ratio, a modified thermal capacity ratio, and a buoyancy or mixed convection parameter. The transformed partial differential equations governing the flow and heat transfer in the f-phase (the macro-pores) and the p-phase (the remainder of the structure) are solved numerically using a very efficient implicit finite-difference technique known as Keller-box method. A good agreement is observed between the present results and those known from the open literature in the special case of a traditional Darcy formulation (monodisperse system).

Intermittent Dynamics, Stochastic Resonance and Dynamical Heterogeneity in Supercooled Liquid Water

Here we find through computer simulations and theoretical analysis that the low temperature thermodynamic anomalies of liquid water arises from the intermittent fluctuation between its high density and low density forms, consisting largely of 5-coordinated and 4-coordinated water molecules, respectively. The fluctuations exhibit strong dynamic heterogeneity (defined by the four point time correlation function), accompanied by a divergence like growth of the dynamic correlation length, of the type encountered in fragile supercooled liquids. The intermittency has been explained by invoking a two state model often employed to understand stochastic resonance, with the relevant periodic perturbation provided here by the fluctuation of the total volume of the system.

Multiphase models for simulating hot and slightly miscible DNAPL (dense non-aqueous phase fluids) in a saturated rock fracture under deformation

In the present study a two dimensional model is first developed to show the behaviour of dense non-aqueous phase liquids (DNAPL) within a rough fracture. To consider the rough fracture, the fracture is imposed with variable apertures along its plane. It is found that DNAPL follows preferential pathways. In next part of the study the above model is further extended for non-isothermal DNAPL flow and DNAPL-water interphase mass transfer phenomenon. These two models are then coupled with joint deformation due to normal stresses. The primary focus of these models is specifically to elucidate the influence of joint alteration due to external stress and fluid pressures on flow driven energy transport and interphase mass transfer. For this, it is assumed that the critical value for joint alteration is associated with external stress and average of water and DNAPL pressures in multiphase system and the temporal and spatial evolution of joint alteration are determined for its further influence on energy transport and miscible phase transfer. The developed model has been studied to show the influence of deformation on DNAPL flow. Further this preliminary study demonstrates the influence of joint deformation on heat transport and phase miscibility via multiphase flow velocities. It is seen that the temperature profile changes and shows higher diffusivity due to deformation and although the interphase miscibility value decreases but the lateral dispersion increases to a considerably higher extent.

Efficient Output-Sensitive Construction of Reeb Graphs

The Reeb graph tracks topology changes in level sets of a scalar function and finds applications in scientific visualization and geometric modeling. This paper describes a near-optimal two-step algorithm that constructs the Reeb graph of a Morse function defined over manifolds in any dimension. The algorithm first identifies the critical points of the input manifold, and then connects these critical points in the second step to obtain the Reeb graph. A simplification mechanism based on topological persistence aids in the removal of noise and unimportant features. A radial layout scheme results in a feature-directed drawing of the Reeb graph. Experimental results demonstrate the efficiency of the Reeb graph construction in practice and its applications.

Ultrafast Solvation Dynamics of an Ion in the gamma-Cyclodextrin Cavity: The Role of Restricted Environment

A detailed study of the solvation dynamics of a charged coumarin dye molecule in gamma-cyclodextrin/water has been carried out by using two different theoretical approaches. The first approach is based on a multishell continuum model (MSCM). This model predicts the time scales of the dynamics rather well, provided an accurate description of the frequency-dependent dielectric function is supplied. The reason for this rather surprising agreement is 2-fold. First, there is a cancellation of errors, second, the two-zone model mimics the heterogeneous microenvironment surrounding the ion rather well. The second approach is based on the molecular hydrodynamics theory (MI-IT). In this molecular approach, the solvation dynamics has been studied by restricting the translational motion of the solvent molecules enclosed within the cavity. The results from the molecular theory are also in good agreement with the experimental results. Our study indicates that, in the present case, the restricted environment affects only the long time decay of the solvation time correlation function. The short time dynamics is still governed by the librational (and/or vibrational) modes present in bulk water.

Hybrid structural control using magnetorheological dampers for base isolated structures

In this paper two nonlinear model based control algorithms have been developed to monitor the magnetorheological (MR) damper voltage. The main advantage of the proposed algorithms is that it is possible to directly monitor the voltage required to control the structural vibration considering the effect of the supplied and commanded voltage dynamics of the damper. The efficiency of the proposed techniques has been shown and compared taking an example of a base isolated three-storey building under a set of seismic excitations. Comparison of the performances with a fuzzy based intelligent control algorithm and a widely used clipped optimal strategy has also been shown.

Small-amplitude cyclic voltammetry: Part I. A simple fourier synthesis approach

Current-potential relationships are derived for small-amplitude periodic inputs for linear electrochemical systems using a Fourier synthesis procedure. Specific results have been obtained for a triangular potential waveform for two simple model systems.

Adsorption isotherms for neutral organic compounds-A hierarchy in modelling: Part II

A two-state model allowing for size disparity between the solvent and the adsorbate is analysed to derive the adsorption isotherm for electrosorption of organic compounds. Explicity, the organic adsorbate is assumed to occupy "n" lattice sites at the interface as compared to "one" by the solvent. The model parameters are the respective permanent and induced dipole moments apart from the nearest neighbour distance. The coulombic interactions due to permanent and induced dipole moments, discreteness of charge effects, and short-range and specific substrate interactions have all been incorporated. The adsorption isotherm is then derived using mean field approximation (MFA) and is found to be more general than the earlier multi-site versions of Bockris and Swinkels, Mohilner et al., and Bennes, as far as the entropy contributions are concerned. The role of electrostatic forces is explicity reflected in the adsorption isotherm via the Gibbs energy of adsorption term which itself is a quadratic function of the electrode charge-density. The approximation implicit in the adsorption isotherm of Mohilner et al. or Bennes is indicated briefly.

Adsorption isotherms-Microscopic modelling: Part II

A lattice formahsm using "spin variables" is employed to analyse multi-state models for the adsorption of neutral dipoles.In particular, a spin-1/2 (two-state) model incorporating permanent and reduced dipole moments of the solvent and the organic adsorbate,substrate interactions, and &screteness of charge effects is analysed The resulting Generalized Islng Hamaltonian is solved under mean field approximation (MFA) in order to derive the adsorption isotherm for organic molecules A few spin-1 (three-state) models are also analysed under MFA to describe the competitive adsorption of multi-state solvent and organic dipoles, and the appropriate equilibrium relations are derived The unification and isomorphism existing at the Hamlltonlan level for several diverse realizations, such as adsorption of ions and solvent/orgamc molecules, is indicated The possibility of analysing phase transitions using this generalized approach is briefly indicated.

ESR studies of non-silicate inorganic glasses through their glass transformation ranges

ESR spectra of three inorganic glasses doped with Mn2+ and Fe3+ have been studied through their glass transition temperatures (Tg). Spectral features in each case have been discussed with reference to site symmetries. The intensity of the ESR signal has been bound to decrease in the region of Tg. An attempt has been made to explain this interesting feature on the basis of a two-state model.

Speckle-based fibre-optic current sensor

A new fibre-optic sensor, based on the speckle phenomenon, for the measurement of current is described. The technique has the advantages of simplicity and sensitivity, but requires a two-step measurement procedure.

The mechanism of manganese electrodeposition

The mechanism of manganese electrodeposition from a sulphate bath on to a stainless-steel substrate has been studied by using current efficiency data to resolve the totali-E curves. A simple, two-step electron transfer mechanism:is proposed to explain the following experimentally obtained parameters: cathodic and anodic transfer coefficients, reaction order and stoichiometric number. The mechanism also explains the effect of pH oni o,Mn and on the corrosion currents.

Determination of optimal trajectory under design constraints for a satellite launch vehicle

An optimal pitch steering programme of a solid-fuel satellite launch vehicle to maximize either (1) the injection velocity at a given altitude, or (2) the size of circular orbit, for a given payload is presented. The two-dimensional model includes the rotation of atmosphere with the Earth, the vehicle's lift and drag, variation of thrust with time and altitude, inverse-square gravitational field, and the specified initial vertical take-off. The inequality constraints on the aerodynamic load, control force, and turning rates are also imposed. Using the properties of the central force motion the terminal constraint conditions at coast apogee are transferred to the penultimate stage burnout. Such a transformation converts a time-free problem into a time-fixed one, reduces the number of terminal constraints, improves accuracy, besides demanding less computer memory and time. The adjoint equations are developed in a compact matrix form. The problem is solved on an IBM 360/44 computer using a steepest ascent algorithm. An illustrative analysis of a typical launch vehicle establishes the speed of convergence, and accuracy and applicability of the algorithm.