A molecular dynamics study of ambient and high pressure phases of silica: Structure and enthalpy variation with molar volume

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, alpha-PbO2-type, and pyrite-type for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase. (C) 2014 AIP Publishing LLC.

Pressure Dependence of Glass Transition in As2Te3 Glass

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (T-g). Generally, application of high pressure increases the T-g and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As2Te3 glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at T-g. The T-g estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 degrees C/kbar for a linear fit and -2.99 degrees C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As2Se3, and As30Se30Te40 show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As2Te3 glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Delta k/Delta alpha will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between T-g and the optical band gap (E-g for covalent semiconducting glasses when they are grouped according to their average coordination number. The electrical band gap (Delta E) of As2Te3 glass decreases with pressure. The optical and electrical band gaps are related as Delta E-g = 2 Delta E; thus, a negative dT(g)/dP is expected when As2Te3 glass is subjected to high pressures. In this sense, As2Te3 is a unique glass where its variation of T-g with pressure can be understood by both electronic and thermodynamic models.

Effect of Process Deviations on Performance of Piezoresistive Pressure Sensors

Diaphragm thickness and the corresponding piezoresistor locations change due to over or under etching in bulk micromachined piezoresistive pressure sensor which intern influences the device performance. In the present work, variation of sensitivity and nonlinearity of a micro electro mechanical system low pressure sensor is investigated. The sensor is modeled using finite element method to analyze the variation of sensitivity and nonlinearity with diaphragm thickness. To verify the simulated results, the sensors with different diaphragm thicknesses are fabricated. The models are verified by comparing the calculated results with experimental data. This study is potentially useful for the researchers as most of the times the diaphragm is either over-etched or under-etched due to inherent variation in wafer thickness and involving manual operations.

Effect of High-Pressure Torsion on Texture, Microstructure, and Raman Spectroscopy: Case Study of Fe- and Te-Substituted CoSb3

Fe0.05Co0.95Sb2.875Te0.125, a double-element-substituted skutterudite, was prepared by induction melting, annealing, and hot pressing (HP). The hot-pressed sample was subjected to high-pressure torsion (HPT) with 4 GPa pressure at 673 K. X-ray diffraction was performed before and after HPT processing of the sample; the skutterudite phase was observed as a main phase, but an additional impurity phase (CoSb2) was observed in the HPT-processed sample. Surface morphology was determined by high-resolution scanning electron microscopy. In the HP sample, coarse grains with sizes in the range of approximately 100 nm to 300 nm were obtained. They changed to fine grains with a reduction in grain size to 75 nm to 125 nm after HPT due to severe plastic deformation. Crystallographic texture, as measured by x-ray diffraction, indicated strengthening of (112), (102) poles and weakening of the (123) pole of the HPT-processed sample. Raman-active vibrational modes showed a peak position shift towards the lower energy side, indicating softening of the modes after HPT. The distortion of the rectangular Sb-Sb rings leads to broadening of Sb-Sb vibrational modes due to local strain fluctuation. In the HPT process, a significant effect on the shorter Sb-Sb bond was observed as compared with the longer Sb-Sb bond.

Observation of Combined Effect of Temperature and Pressure on Cubic to Hexagonal Phase Transformation in ZnS at the Nanoscale

The temperature of allotropic phase transformation in ZnS (cubic to wurtzite) changes with pressure and particle size. In this paper we have explored the interrelation among these through a detailed study of ZnS powders obtained by a temperature-controlled high energy milling process. By employing the combined effect of temperature and pressure in an indigenously built cryomill, we have demonstrated a large-scale, low-temperature synthesis of wurtzite ZnS nanoparticles. The synthesized products have been characterized for their phase and microstructure by the use of X-ray diffraction and transmission electron microscopic techniques. Further, it has been demonstrated that the synthesized materials exhibit photoluminescence emissions in the UV-visible region with an unusual doublet pattern due to the presence of both cubic and hexagonal wurtzite domains in the same particles. By further fine-tuning the processing conditions, it may be possible to achieve controlled defect related photoluminescence emissions from the ZnS nanoparticles.

Enhancement in threshold voltage with thickness in memory switch fabricated using GeSe1.5S0.5 thin films

Investigations on the electrical switching, structural, optical and photoacoustic analysis have been undertaken on chalcogenide GeSe1.5S0.5 thin films of various thicknesses prepared by vacuum evaporation technique. The decrease of band gap energy with increase in film thickness has been explained using the `density of states model'. The structural units of the films are characterized using Raman spectroscopy and the deconvoluted Raman peaks obtained from Gaussian fit around 188 cm(-1), 204 cm(-1) and 214 cm(-1) favors Ge-chalcogen tetrahedral units forming corner and edge sharing tetrahedra. All the thin films samples have been exhibited memory-type electrical switching behavior. An enhancement in the threshold voltages of GeSe1.5S0.5 thin films have been observed with increase in film thickness. The thickness dependence of switching voltages provide an insight into the switching mechanism and it is explained by the Joule heating effect. (C) 2014 Elsevier B.V. All rights reserved.

Breakup processes of pressure swirl spray in gaseous cross-flow

Injection of liquid fuel in cross flowing air has been a strategy for future aircraft engines in order to control the emissions. In this context, breakup of a pressure swirl spray in gaseous cross-flow is investigated experimentally. The atomizer discharges a conical swirling sheet of liquid that interacts with cross-flowing air. This complex interaction and the resulting spray structures at various flow conditions are studied through flow visualization using still as well as high speed photography. Experiments are performed over a wide range of aerodynamic Weber number (2-300) and liquid-to-air momentum flux ratio (5-150). Various breakup regimes exhibiting different breakup processes are mapped on a parameter space based on flow conditions. This map shows significant variations from breakup regime map for a plain liquid jet in cross-flow. It is observed that the breakup of leeward side of the sheet is dominated by bag breakup and the windward side of the sheet undergoes breakup through surface waves. Similarities and differences between bag breakup present in plain liquid jet in cross-flow and swirl spray in cross-flow are explained. Multimodal drop size distribution from bag breakup, frequency of bag breakup, wavelength of surface waves and trajectory of spray in cross-flow are measured by analyzing the spray images and parametric study of their variations is also presented. (C) 2014 Elsevier Ltd. All rights reserved.

An improved free surface modeling for incompressible SPH

In Incompressible Smooth Particle Hydrodynamics (ISPH), a pressure Poisson equation (PPE) is solved to obtain a divergence free velocity field. When free surfaces are simulated using this method a Dirichlet boundary condition for pressure at the free surface has to be applied. In existing ISPH methods this is achieved by identifying free surface particles using heuristically chosen threshold of a parameter such as kernel sum, density or divergence of the position, and explicitly setting their pressure values. This often leads to clumping of particles near the free surface and spraying off of surface particles during splashes. Moreover, surface pressure gradients in flows where surface tension is important are not captured well using this approach. We propose a more accurate semi-analytical approach to impose Dirichlet boundary conditions on the free surface. We show the efficacy of the proposed algorithm by using test cases of elongation of a droplet and dam break. We perform two dimensional simulations of water entry and validate the proposed algorithm with experimental results. Further, a three dimensional simulation of droplet splash is shown to compare well with the Volume-of-Fluid simulations. (C) 2014 Elsevier Ltd. All rights reserved.

High pressure studies on the electrical resistivity of Ge-Te-Tl glasses

The variation of electrical resistivity in the system of glasses Ge17Te83-xTlx, with (1 <= x <= 13), has been studied as a function of high pressure for pressures up to 10 GPa. It is found that the normalized electrical resistivity decreases continuously with the increase in pressure and shows a sudden drop at a particular pressure (transition pressure), indicating the presence of a transition from semiconductor to near-metallic at these pressures which are in the range 3.0-5.0 GPa. This transition pressure is seen to decrease with the increase in the percentage content of thallium due to increasing metallicity of the thallium. The transition is reversible under application of pressure and X-ray diffraction of samples recovered after pressurization show that they remain amorphous after undergoing a pressurization decompression cycle.

Pressure induced manifold enhancement of Li-kinetics in FCC fullerene

The reduction of the diffusion energy barrier for Li in electrodes is one of the required criteria to achieve better performances in Li ion batteries. Using density functional theory based calculations, we report a pressure induced manifold enhancement of Li-kinetics in bulk FCC fullerene. Scanning of the potential energy surface reveals a diffusion path with a low energy barrier of 0.62 eV, which reduces further under the application of hydrostatic pressure. The pressure induced reduction in the diffusion barrier continues till a uniform volume strain of 17.7% is reached. Further enhancement of strain increases the barrier due to the repulsion caused by C-C bond formation between two neighbouring fullerenes. The decrease in the barrier is attributed to the combined effect of charge transfer triggered by the enhanced interaction of Li with the fullerene as well as the change in profile of the local potential, which becomes more attractive for Li. The lowering of the barrier leads to an enhancement of two orders of magnitude in Li diffusivity at room temperature making pressurized bulk fullerene a promising artificial solid electrolyte interface (SEI) for a faster rechargeable battery.

Experimental and theoretical studies on static and dynamic pressure-concentration isotherms of MmNi(5-x)Al(x) (x=0, 0.3, 0.5 and 0.8) hydrides

The static and dynamic pressure concentration isotherms (PCIs) of MmNi(5-x)Al(x). (x = 0, 0.3, 0.5 and 0.8) hydrides were measured at different temperatures using volumetric method. The effect of Al substitution on PCI and thermodynamic properties were studied. The plateau pressure and maximum hydrogen storage capacity decreased with Al content whereas reaction enthalpy increased. The plateau pressure, plateau slope and hysteresis effect was observed more for dynamic PCIs compared to static PCIs. Different mathematical models used for metal hydride-based thermodynamic devices simulation are compared to select suitable model for static and dynamic PCI simulation of MmNi(5)-based hydrides. Few important physical coefficients (partial molar volume, reaction enthalpy, reaction entropy, etc.) useful for development of thermodynamic devices were estimated. A relation has been proposed to correlate aluminium content and physical coefficients for the prediction of unknown PCI. The simulated and experimental PCIs were found matching closely for both static and dynamic conditions. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Investigations on pressure and thickness profiles in carbon fiber-reinforced polymers during vacuum assisted resin transfer molding

Systematic experiments have been carried out by monitoring the in-situ pressure and thickness profiles for three different configurations, viz., flat plate, flat plate with a central circular hole, and an L-section using vacuum assisted resin transfer molding (VARTM) process. The effect of anisotropy on resin flow has been quantified by considering uni-directional carbon fiber preforms with 0 degrees and 90 degrees orientation to the flow direction for each configuration. A quasi-isotropic 45 degrees/0 degrees/-45 degrees/90 degrees](S) layup has also been included for flat plate case. Additionally, the study has been extended to understand the effect of using high permeability medium for each configuration. Fluid pressure profiles and thickness variation profiles have been obtained using an array of pressure sensors and linear variable differential transformers for each configuration. Experimental data reveal that anisotropy (due to changing fiber orientations), configuration, and gravity significantly change fluid pressure and displacement fields obtained during VARTM.

On flame-turbulence interaction in constant-pressure expanding flames

In this paper we present one of the first high-speed particle image velocimetry measurements to quantify flame-turbulence interaction in centrally-ignited constant-pressure premixed flames expanding in nearisotropic turbulence. Measurements of mean flow velocity and rms of fluctuating flow velocity are provided over a range of conditions both in the presence and absence of the flame. The distributions of stretch rate contributions from different terms such as tangential straining, normal straining and curvature are also provided. It is found that the normal straining displays non-Gaussian pdf tails whereas the tangential straining shows near Gaussian behavior. We have further tracked the motion of the edge points that reside and co-move with the edge of the flame kernel during its evolution in time, and found that within the measurement conditions, on average the persistence time scales of stretch due to pure curvature exceed that due to tangential straining by at least a factor of two. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Pressure-Dependent Optical and Vibrational Properties of Mono layer Molybdenum Disulfide

Controlling the band gap by tuning the lattice structure through pressure engineering is a relatively new route for tailoring the optoelectronic properties of two-dimensional (2D) materials. Here, we investigate the electronic structure and lattice vibrational dynamics of the distorted monolayer 1T-MoS2 (1T') and the monolayer 2H-MoS2 via a diamond anvil cell (DAC) and density functional theory (DFT) calculations. The direct optical band gap of the monolayer 2H-MoS2 increases by 11.7% from 1.85 to 2.08 eV, which is the highest reported for a 2D transition metal dichalcogenide (TMD) material. DFT calculations reveal a subsequent decrease in the band gap with eventual metallization of the monolayer 2H-MoS2, an overall complex structureproperty relation due to the rich band structure of MoS2. Remarkably, the metastable 1T'-MoS2 metallic state remains invariant with pressure, with the J(2), A(1g), and E(2)g modes becoming dominant at high pressures. This substantial reversible tunability of the electronic and vibrational properties of the MoS2 family can be extended to other 2D TMDs. These results present an important advance toward controlling the band structure and optoelectronic properties of monolayer MoS2 via pressure, which has vital implications for enhanced device applications.

Thermally developing combined electroosmotic and pressure-driven flow of nanofluids in a microchannel under the effect of magnetic field

In the present study, the heat transfer characteristics of thermally developing magnetohydroclynamic flow of nanofluid through microchannel are delineated by following a semi analytical approach. The combined influences of pressure driven flow, electroosmotic transport and magnetic field is taken into account for the analysis of the complex microscale thermal transport processes. Solutions for the normalized temperature distributions and the Nusselt number variations, considering the simultaneous interplay of electrokinetic effects (electroosmosis), magnetic effects, Joule heating and viscous dissipation are obtained, for constant wall temperature condition. Particular attention is paid to assess the role of nanolluids in altering the transport phenomena, through variations in the effective nanoparticle volume fractions, as well as the aggregate structure of the particulate phases. It is observed that magnetohydrodynamic effect reduces advective transport of the liquid resulting in gradual reduction of heat transfer. Increase in nanoparticle volume fraction shows decrease in heat transfer. Similar effects are observed with increase in aggregate sizes of the nanoparticles. The effect of the nanofluids on system irreversibility is also studied through entropy generation analysis due to flow and heat transfer in the microchannel. Total entropy generation is found to be dominant at the thermally developing region of the microchannel, whereas it drops sharply at the thermally developed region. Presence of nanoparticles in the base fluid reduces the total entropy generation in the microchannel, thereby indicating decrease in thermodynamic irreversibility with increasing nanoparticle volume fraction. (C) 2014 Elsevier Ltd. All rights reserved.