System Gd-Rh-O: Thermodynamics and phase relations

Thermodynamic properties of GdRhO3 are investigated in the temperature range from 900 to 1300 K by employing a solid-state electrochemical cell, incorporating calcia-stabilized zirconia as the electrolyte. The standard Gibbs free energy of formation of GdRhO3 from component binary oxide Gd2O3 with C-rare earth structure and Rh2O3 with orthorhombic structure can be expressed as; Delta G(f(ox))(o)(+/- 60)/J mol(-1) = -56603 + 3.78(T/K) Based on the thermodynamic information on GdRhO3 from experiment and auxiliary data for binary oxides from the literature and estimated properties of Gd-Rh alloys, phase relations are computed for the system Gd-Rh-O at 1273 K. Gibbs free energies for intermetallic phases in the binary Gd-Rh are evaluated using calorimetric data available in the literature for two compositions and Miedema's model, consistent with the binary phase diagram. Isothermal section of the ternary phase diagram, oxygen potential-composition diagram and a 3-D chemical potential diagram for the system Gd-Rh-O at 1273 K are developed. Phase relations in the ternary Gd-Rh-O are also computed as a function of temperature at constant oxygen partial pressures. The ternary oxide, GdRhO3 decomposes to Gd2O3 with B-rare earth structure, metallic Rh and O-2 at 1759(+/- 2) K in pure O-2 and 1649(+/- 2) K in air at a total pressure P-0 -0.1 MPa. (c) 2012 Elsevier B.V. All rights reserved.

System Reliability Analysis of Flexible Pavements

The uncertainty in material properties and traffic characterization in the design of flexible pavements has led to significant efforts in recent years to incorporate reliability methods and probabilistic design procedures for the design, rehabilitation, and maintenance of pavements. In the mechanistic-empirical (ME) design of pavements, despite the fact that there are multiple failure modes, the design criteria applied in the majority of analytical pavement design methods guard only against fatigue cracking and subgrade rutting, which are usually considered as independent failure events. This study carries out the reliability analysis for a flexible pavement section for these failure criteria based on the first-order reliability method (FORM) and the second-order reliability method (SORM) techniques and the crude Monte Carlo simulation. Through a sensitivity analysis, the most critical parameter affecting the design reliability for both fatigue and rutting failure criteria was identified as the surface layer thickness. However, reliability analysis in pavement design is most useful if it can be efficiently and accurately applied to components of pavement design and the combination of these components in an overall system analysis. The study shows that for the pavement section considered, there is a high degree of dependence between the two failure modes, and demonstrates that the probability of simultaneous occurrence of failures can be almost as high as the probability of component failures. Thus, the need to consider the system reliability in the pavement analysis is highlighted, and the study indicates that the improvement of pavement performance should be tackled in the light of reducing this undesirable event of simultaneous failure and not merely the consideration of the more critical failure mode. Furthermore, this probability of simultaneous occurrence of failures is seen to increase considerably with small increments in the mean traffic loads, which also results in wider system reliability bounds. The study also advocates the use of narrow bounds to the probability of failure, which provides a better estimate of the probability of failure, as validated from the results obtained from Monte Carlo simulation (MCS).

A two-axis in-plane motion measurement system based on optical beam deflection

Measurement of in-plane motion with high resolution and large bandwidth enables model-identification and real-time control of motion-stages. This paper presents an optical beam deflection based system for measurement of in-plane motion of both macro- and micro-scale motion stages. A curved reflector is integrated with the motion stage to achieve sensitivity to in-plane translational motion along two axes. Under optimal settings, the measurement system is shown to theoretically achieve sub-angstrom measurement resolution over a bandwidth in excess of 1 kHz and negligible cross-sensitivity to linear motion. Subsequently, the proposed technique is experimentally demonstrated by measuring the in-plane motion of a piezo flexure stage and a scanning probe microcantilever. For the former case, reflective spherical balls of different radii are employed to measure the in-plane motion and the measured sensitivities are shown to agree with theoretical values, on average, to within 8.3%. For the latter case, a prototype polydimethylsiloxane micro-reflector is integrated with the microcantilever. The measured in-plane motion of the microcantilever probe is used to identify nonlinearities and the transient dynamics of the piezo-stage upon which the probe is mounted. These are subsequently compensated by means of feedback control. (C) 2013 AIP Publishing LLC.

Solid-solid collapse transition in a two dimensional model molecular system

Solid-solid collapse transition in open framework structures is ubiquitous in nature. The real difficulty in understanding detailed microscopic aspects of such transitions in molecular systems arises from the interplay between different energy and length scales involved in molecular systems, often mediated through a solvent. In this work we employ Monte-Carlo simulation to study the collapse transition in a model molecular system interacting via both isotropic as well as anisotropic interactions having different length and energy scales. The model we use is known as Mercedes-Benz (MB), which, for a specific set of parameters, sustains two solid phases: honeycomb and oblique. In order to study the temperature induced collapse transition, we start with a metastable honeycomb solid and induce transition by increasing temperature. High density oblique solid so formed has two characteristic length scales corresponding to isotropic and anisotropic parts of interaction potential. Contrary to the common belief and classical nucleation theory, interestingly, we find linear strip-like nucleating clusters having significantly different order and average coordination number than the bulk stable phase. In the early stage of growth, the cluster grows as a linear strip, followed by branched and ring-like strips. The geometry of growing cluster is a consequence of the delicate balance between two types of interactions, which enables the dominance of stabilizing energy over destabilizing surface energy. The nucleus of stable oblique phase is wetted by intermediate order particles, which minimizes the surface free energy. In the case of pressure induced transition at low temperature the collapsed state is a disordered solid. The disordered solid phase has diverse local quasi-stable structures along with oblique-solid like domains. (C) 2013 AIP Publishing LLC.

Phase equilibria in the system Sm-Rh-O and thermodynamic and thermal studies on SmRhO3

Using isothermal equilibration, phase relations are established in the system Sm-Rh-O at 1273 K. SmRhO3 with GdFeO3-type perovskite structure is found to be the only ternary phase. Solid-state electrochemical cells, containing calcia-stabilized zirconia as an electrolyte, are used to measure the thermodynamic properties of SmRhO3 formed from their binary component oxides Rh2O3 (ortho) and Sm2O3 (C-type and B-type) in two different temperature ranges. Results suggest that C-type Sm2O3 with cubic structure transforms to B-type Sm2O3 with monoclinic structure at 1110 K. The standard Gibbs energy of transformation is . Standard Gibbs energy of formation of SmRhO3 from binary component oxides Rh2O3 and Sm2O3 with B-type rare earth oxide structure can be expressed as . The decomposition temperature of SmRhO3 estimated from the extrapolation of electrochemical data is 1665 (+/- 2) K in air and 1773 (+/- 3) K in pure oxygen. Temperature-composition diagrams at constant oxygen pressures are constructed for the system Sm-Rh-O. Employing the thermodynamic data for SmRhO3 from emf measurement and auxiliary data for other phases from the literature, oxygen potential-composition phase diagram and 3-D chemical potential diagram for the system Sm-Rh-O at 1273 K are developed.

Laterally structured ripple and square phases with one and two dimensional thickness modulations in a model bilayer system

Molecular dynamics simulations of bilayers in a surfactant/co-surfactant/water system with explicit solvent molecules show formation of topologically distinct gel phases depending upon the bilayer composition. At low temperatures, the bilayers transform from the tilted gel phase, L beta', to the one dimensional (1D) rippled, P beta' phase as the surfactant concentration is increased. More interestingly, we observe a two dimensional (2D) square phase at higher surfactant concentration which, upon heating, transforms to the gel L beta' phase. The thickness modulations in the 1D rippled and square phases are asymmetric in two surfactant leaflets and the bilayer thickness varies by a factor of similar to 2 between maximum and minimum. The 1D ripple consists of a thinner interdigitated region of smaller extent alternating with a thicker non-interdigitated region. The 2D ripple phase is made up of two superimposed square lattices of maximum and minimum thicknesses with molecules of high tilt forming a square lattice translated from the lattice formed with the thickness minima. Using Voronoi diagrams we analyze the intricate interplay between the area-per-head-group, height modulations and chain tilt for the different ripple symmetries. Our simulations indicate that composition plays an important role in controlling the formation of low temperature gel phase symmetries and rippling accommodates the increased area-per-head-group of the surfactant molecules.

Phase relations in the system Ca-Ta-O and thermodynamics of calcium tantalates in relation to calciothermic reduction of Ta2O5

Phase equilibria of the system Ca-Ta-O is established by equilibrating eleven samples at 1200 K for prolonged periods and phase identification in quenched samples by optical and scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Four ternary oxides are identified: CaTa4O11, CaTa2O6, Ca2Ta2O7 and Ca4Ta2O9. Isothermal section of the phase diagram is composed using the results. Thermodynamic properties of the ternary oxides are measured in the temperature range from 975 to 1275 K employing solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells essentially measure the chemical potentials of CaO in two-phase fields (Ta2O5 + CaTa4O11), (CaTa4O11 + CaTa2O6), (CaTa2O6 + Ca2Ta2O7), and (Ca2Ta2O7 + Ca4Ta2O9) of the pseudo-binary system CaO-Ta2O5. The standard Gibbs energies of formation of the four ternary oxides from their component binary oxides Ta2O5 and CaO are given by: Delta G(f)((ox))(o) (CaTa4O11) (+/- 482)/J mol(-1) = -58644+21.497 (T/K) Delta G(f)((ox))(o) (CaTa2O6) (+/- 618)/J mol(-1) = -55122+21.893 (T/K) Delta G(f)((ox))(o) (Ca2Ta2O7) (+/- 729)/J mol(-1) = -82562+31.843 (T/K) Delta G(f)((ox))(o) (Ca4Ta2O9) (+/- 955)/J mol(-1) = -126598+48.859 (T/K) The Gibbs energy of formation of the four ternary compounds obtained in this study differs significantly from that reported in the literature. The thermodynamic data and phase diagram are used for understanding the mechanism and kinetics of calciothermic and electrochemical reduction of Ta2O5 to metal. (C) 2014 Elsevier B.V. All rights reserved.

MRT Letter: Two-Photon Excitation-Based 2pi Light-Sheet System for Nano-Lithography

We propose two-photon excitation-based light-sheet technique for nano-lithography. The system consists of 2 -configured cylindrical lens system with a common geometrical focus. Upon superposition, the phase-matched counter-propagating light-sheets result in the generation of identical and equi spaced nano-bump pattern. Study shows a feature size of as small as few tens of nanometers with a inter-bump distance of few hundred nanometers. This technique overcomes some of the limitations of existing nano-lithography techniques, thereby, may pave the way for mass-production of nano-structures. Potential applications can also be found in optical microscopy, plasmonics, and nano-electronics. Microsc. Res. Tech. 78:1-7, 2015. (c) 2014 Wiley Periodicals, Inc.

Observation of coherent population trapping in a V-type two-electron system

We observe coherent population trapping (CPT) in a two-electron atom-Yb-174-using the S-1(0), F= 0 -> P-3(1), F `= 1 transition. CPT is not possible for such a transition according to one-electron theory because the magnetic sublevels form a V-type system, but in a two-electron atom like Yb, the interaction of the electrons transforms the level structure into a V-type system, which allows the formation of a dark state and hence the observation of CPT. Since the two levels involved are degenerate, we use a magnetic field to lift the degeneracy. The single fluorescence dip then splits into five dips-the central unshifted one corresponds to coherent population oscillation, while the outer four are due to CPT. The linewidth of the CPT resonance is about 300 kHz and is limited by the natural linewidth of the excited state, which is to be expected because the excited state is involved in the formation of the dark state.

Performance evaluation of a two-stage silica gel plus water adsorption based cooling-cum-desalination system

The first objective of this paper is to show that a single-stage adsorption based cooling-cum-desalination system cannot be used if air cooled heat rejection is used under tropical conditions. This objective is achieved by operating a silica gel + water adsorption chiller first in a single-stage mode and then in a 2-stage mode with 2 beds/stage in each case. The second objective is to improve upon the simulation results obtained earlier by way of empirically describing the thermal wave phenomena during switching of operation of beds between adsorption and desorption and vice versa. Performance indicators, namely, cooling capacity, coefficient of performance and desalinated water output are extracted for various evaporator pressures and half cycle times. The improved simulation model is found to interpret experimental results more closely than the earlier one. Reasons for decline in performance indicators between theoretical and actual scenarios are appraised. (C) 2015 Elsevier Ltd and IIR. All rights reserved.

Instrumentation and control of a two-stage 4-bed silica gel plus water adsorption cooling cum desalination system

This paper presents the instrumentation and control architecture for a laboratory based two-stage 4-bed silica gel + water adsorption system. The system consists of primarily two fluids: refrigerant (water vapour) and heat transfer fluid (water) flowing through various components. Heat input to the system is simulated using multiple heaters and ambient air is used as the heat sink. The laboratory setup incorporates a real time National Instruments (NI) controller to control several digital and analog valves, heaters, pumps and fans along with simultaneous data acquisition from various flow, pressure and temperature sensors. The paper also presents in detail the various automated and manual tasks required for successful operation of the system. Finally the system pressure and temperature dynamics are reported and its performance evaluated for various cycle times. (C) 2015 Elsevier Ltd. All rights reserved.