Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

Vapour phase synthesis of salol over solid acids via transesterification

The transesterification of methyl salicylate with phenol has been studied in vapour phase over solid acid catalysts such as ZrO2, MoO3 and SO42- or Mo(VI) ions modified zirconia. The catalytic materials were prepared and characterized for their total surface acidity, BET surface area and powder XRD patterns. The effect of mole-ratio of the reactants, catalyst bed temperature, catalyst weight, flow-rate of reactants, WHSV and time-on-stream on the conversion (%) of phenol and selectivity (%) of salol has been investigated. A good yield (up to 70%) of salol with 90% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200 degrees C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of SO42- or Mo(VI) ions. The effect of poisoning of acid sites of SO42- or Mo(VI) ions modified zirconia on total surface acidity, powder XRD phases and catalytic activity was also studied. Possible reaction mechanisms for the formation of salol and diphenyl ether over acid sites are proposed.

Singularity and controllability analysis of parallel manipulators and closed-loop mechanisms

This paper presents a study of kinematic and force singularities in parallel manipulators and closed-loop mechanisms and their relationship to accessibility and controllability of such manipulators and closed-loop mechanisms, Parallel manipulators and closed-loop mechanisms are classified according to their degrees of freedom, number of output Cartesian variables used to describe their motion and the number of actuated joint inputs. The singularities in the workspace are obtained by considering the force transformation matrix which maps the forces and torques in joint space to output forces and torques ill Cartesian space. The regions in the workspace which violate the small time local controllability (STLC) and small time local accessibility (STLA) condition are obtained by deriving the equations of motion in terms of Cartesian variables and by using techniques from Lie algebra.We show that for fully actuated manipulators when the number ofactuated joint inputs is equal to the number of output Cartesian variables, and the force transformation matrix loses rank, the parallel manipulator does not meet the STLC requirement. For the case where the number of joint inputs is less than the number of output Cartesian variables, if the constraint forces and torques (represented by the Lagrange multipliers) become infinite, the force transformation matrix loses rank. Finally, we show that the singular and non-STLC regions in the workspace of a parallel manipulator and closed-loop mechanism can be reduced by adding redundant joint actuators and links. The results are illustrated with the help of numerical examples where we plot the singular and non-STLC/non-STLA regions of parallel manipulators and closed-loop mechanisms belonging to the above mentioned classes. (C) 2000 Elsevier Science Ltd. All rights reserved.

Electron diffraction patterns from the Al-Mn decagonal phase

The variety of electron diffraction patterns arising from the decagonal phase has been explored using a stereographic analysis for generating the important zone axes as intersection points corresponding to important relvectors. An indexing scheme employing a set of five vectors and an orthogonal vector has been followed. A systematic tilting from the decagonal axis to one of the twofold axes has been adopted to generate a set of experimental diffraction patterns corresponding to the expected patterns from the stereographic analysis with excellent agreement.

Effect of mode of rolling on development of texture and microstructure in two-phase (alpha plus beta) brass

The evolution of microstructure and texture during deformation of two-phase (alpha + beta) brass was studied for different initial microstructure and texture. The deformation processing involved unidirectional and multi-step cross-rolling. The bulk textures were determined by measuring the pole figures and calculating the orientation distribution function ODF for both alpha (fcc) and beta (bcc) phases, while the microstructure and other microstructural parameters were measured through optical microscopy and scanning electron microscopy with electron back scatter diffraction (SEM-EBSD). Results indicate that textures developed after unidirectional rolling and multi-step cross-rolling are significantly different. The variation in initial texture had a pronounced effect on the development of texture in the alpha phase during subsequent deformation. (C) 2010 Elsevier B.V. All rights reserved.

Multi power port converter for hybrid electric vehicles using multi phase bidirectional fly-back topology

For hybrid electric vehicles the batteries and the drive dc-link may be at different voltages. The batteries are at low voltage to obtain higher volumetric efficiencies and the dc-link is at higher voltage to have higher efficiency on the motor side. Therefore a power interface between the batteries and the drive's dc-link is essential. This power interface should handle power flow from battery to motor, motor to battery, external genset to battery and grid to battery. This paper proposes a multi power port topology which is capable of handling multiple power sources and still maintains simplicity and features like obtaining any gain, wide load variations, lower output current ripple and capability of parallel battery energy due to the modular structure. The development and testing of a bi-directional fly-back DC-DC converter for hybrid electric vehicle is described in this paper. Simple hysteresis voltage control is used for DC link voltage regulation. The experimental results are presented to show the working of the proposed converter.

Orbital evolution and orbital phase resolved spectroscopy of the HMXB pulsar 4U 1538-52 with RXTE-PCA and BeppoSAX

We report here results from detailed timing and spectral studies of the high mass X-ray binary pulsar 4U 1538-52 over several binary periods using observations made with the Rossi X-ray Timing Explorer (RXTE) and BeppoSAX satellites. Pulse timing analysis with the 2003 RXTE data over two binary orbits confirms an eccentric orbit of the system. Combining the orbitial parameters determined from this observation with the earlier measurements we did not find any evidence of orbital decay in this X-ray binary. We have carried out orbital phase resolved spectroscopy to measure changes in the spectral parameters with orbital phase, particularly the absorption column density and the iron line flux. The RXTE-PCA spectra in the 3-20 keV energy range were fitted with a power law and a high energy cut-off along with a Gaussian line at similar to 6.4 keV, whereas the BeppoSAX spectra needed only a power law and Gaussian emission line at similar to 6.4keV in the restricted energy range of 0.3-10.0 keV. An absorption along the line of sight was included for both the RXTE and BeppoSAX data. The variation of the free spectral parameters over the binary orbit was investigated and we found that the variation of the column density of absorbing material in the line of sight with orbital phase is in reasonable agreement with a simple model of a spherically symmetric stellar wind from the companion star.

Stress induced phase transition in monomolecular perfluroalkylsilane film self assembled on aluminium surface

We control the stiffnesses of two dual double cantelevers placed in series to control penetration into a perflurooctyltrichlorosilane monolayer self assembled on aluminium and silicon substrates. The top cantilever which carries the probe is displaced with respect to the bottom cantilever which carries the substrate, the difference in displacement recorded using capacitors gives penetration. We further modulate the input displacement sinusoidally to deconvolute the viscoelastic properties of the monolayer. When the intervention is limited to the terminal end of the molecule there is a strong viscous response in consonance with the ability of the molecule to dissipate energy by the generation of gauche defects freely. When the intervention reaches the backbone, at a contact mean pressure of 0.2GPa the damping disappears abruptly and the molecule registers a steep rise in elastic modulus and relaxation time constant, with increasing contact pressure. We offer a physical explanation of the process and describe this change as due to a phase transition from a liquid like to a solid like state.

Electronic phase separation in correlated oxides: The phenomenon, its present status and future prospects

Many transition metal oxide materials of high chemical purity are not necessarily monophasic. Thus, single crystals of chemically pure rare earth manganites and cobaltates of the general formula Ln1-xAxMO3 (Ln=rare earth metal, A=alkaline earth metal, M=Mn, Co) exhibit the phenomenon of electronic phase separation wherein phases of different electronic and magnetic properties coexist. Such phase separation, the length scale of which can vary anywhere between a few nanometers to microns, gives distinct signatures in X-ray and neutron diffraction patterns, electrical and magnetic properties, as well as in NMR and other spectroscopies. While the probe one employs to investigate electronic phase separation depends on the length scale, it is noteworthy that direct imaging of the inhomogeneities has been accomplished. Some understanding of this phenomenon has been possible on the basis of some of the theoretical models, but we are far from unraveling the varied aspects of this new phenomenon. Herein, we present the highlights of experimental techniques and theoretical approaches, and comment on the future outlook for this fascinating phenomenon

Nonlinear intrinsic instability of solid propellant combustion including gas-phase thermal inertia

The problem of homogeneous solid propellant combustion instability is studied with a one-dimensional flame model, including the effects of gas-phase thermal inertia and nonlinearity. Computational results presented in this paper show nonlinear instabilities inherent in the equations, due to which periodic burning is found even under steady ambient conditions such as pressure. The stability boundary is obtained in terms of Denison-Baum parameters. It is found that inclusion of gas-phase thermal inertia stabilizes the combustion. Also, the effect of a distributed heat release in the gas phase, compared to the flame sheet model, is to destabilize the burning. Direct calculations for finite amplitude pressure disturbances show that two distinct resonant modes exist, the first one near the natural frequency as obtained from intrinsic instability analysis and a second mode occurring at a much higher driving frequency. It is found that er rn in the low frequency region, the response of the propellant is significantly affected by the specific type of gas-phase chemical heat-release model employed. Examination of frequency response function reveals that the role of gas-phase thermal inertia is to stabilize the burning near the first resonant mode. Calculations made for different amplitudes of driving pressure show that the mean burning rate decreases with increasing amplitude. Also, with an increase in the driving amplitude, higher harmonics are generated in the burning rate.

Phase diagram and dielectric studies of binary organic materials

The phase equilibrium studies of organic system, involving resorcinol (R) and p-dimethylaminobenzaldehyde (DMAB), reveal the formation of a 1:1 molecular complex with two eutectics. The heat of mixing, entropy of fusion, roughness parameter, interfacial energy, and the excess thermodynamic functions were calculated based on enthalpy of fusion data determined via differential scanning calorimetric (DSC) method. X-ray powder diffraction studies confirm that the eutectics are not simple mechanical mixture of the components under investigation. The spectroscopic investigations (IR and NMR) suggest the occurrence of hydrogen bonding between the components forming the molecular complex. The dielectric measurements, carried out on hot-pressed addition compound (molecular complex), show higher dielectric constant at 320 K than that of individual components. The microstructural investigations of eutectic and addition compound indicate dendritic and faceted morphological features. (C) 2000 Elsevier Science B.V. All rights reserved.

Electronic-Transitions In Hydrogen-Bonded Dimers Of Carboxylic-Acids In The Vapor-Phase - An Electron-Energy Loss Spectroscopic Study

An electron energy loss spectroscopic study of the formic acid dimer has shown bands centred around 7.2, 8.5, 9.8, and 11.1 eV, of which the first and the third bands are assigned to n- rc* transitions and the other two to n-n* transitions; similar transitions are found in the acetic acid dimer.

Phase relations and thermodynamic properties of compounds in the pseudobinary system BaO-Y2O3

The coexisting phases in the pseudobinary system BaO-Y2O3 have been identified by equilibrating samples containing different amounts of component oxides at 1173, 1273 and 1373 K. Only two ternary oxides, BaY2O4 and Ba3Y4O9, have been found to be stable in the temperature range of investigation. Solid state galvanic cells: Pt, O2+BaO+BaF2double vertical barBaF2+2mol%Al2O3double vertical barBaF2+BaY2O4+Y2O3+O2, Pt and Pt, O2+BaO+BaF2double vertical barBaF2+2mol% Al2O3double vertical barBaF2+BaY2O4+Ba3Y4O9+O2, Pt have been employed for determining the Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from the component oxides in the range 850 to 1250 K. A composite solid electrolyte incorporating Al2O3-dispersed BaF2 was used in the cells. To prevent interaction between the Al2O3 powder and electrode materials, the solid electrolyte was coated with pure BaF2. The Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from component oxides are given by: Δf0 (BaY2O4, s)=−128,310+5.211T (±580) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K) and ΔGfo(Ba3Y4O9, s)= −317,490 −24.704T (±1100) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K).

Critical micelle concentration from a lattice gas model

The temperature dependence of the critical micelle concentration (CMC) and a closed-loop coexistence curve are obtained, via Monte Carlo simulations, in the water surfactant limit of a two-dimensional version of a statistical mechanical model for micro-emulsions, The CMC and the coexistence curve reproduce various experimental trends as functions of the couplings. In the oil-surfactant limit, there is a conventional coexistence cure with an upper consolute point that allows for a region of three-phase coexistence between oil-rich, water-rich and microemulsion phases.