Electrochemical measurement of the oxygen potential of the system iron+alumina+ hercynite in the temperature range 750 to 1600oC

Solid oxide galvanic cells using CaO-ZrO2 and CaO-ZrO2 in combination with YO1.5-ThO2 as electrolyte were used to determine the free energy of formation of hercynite from 750–1600°C. The formation reaction is 2Fe(s,1) + O2(g) + Al2O3(α) = 2FeO.Al2O3(s)for which ΔG° = − 139,790 + 32.83T (±300) cals. (750–1536°C) ΔG° = − 146,390 + 36.48T (±300) cals. (1536–1700°C)These measurements can be used to resolve the discrepancies that exist in published thermochemical data, and provide an accurate oxygen potential standard for calibrating and assessing the performance of oxygen probes under steelmaking conditions.

The oxygen potential of the systems Fe+FeCr2O4+ Cr2O3 and Fe+FeV2O4+ V2O3 in the temperature range 750 1600o C

From electromotive force (emf) measurements using solid oxide galvanic cells incorporating ZrOz-CaO and ThOz-YO~.s electrolytes, the chemical potentials of oxygen over the systems Fe + FeCrzO 4 + Cr20 ~ and Fe + FeV204 + V203 were calculated. The values may be represented by the equations: 2Fe(s, I) + Oz(g) + 2Cr2Oa(s) -- 2FeCr204 (s)Akto2 = - 151,400 + 34.7T (• cal= -633,400 + 145.5T(• J (750 to 1536~ A~tO2 = -158,000 + 38.4T(• cal= -661,000 + 160.5T(*1250) J (1536 to 1700~2Fe (s, I) + O2 (g) + 2V203 (s) -- 2FeV204 (s) A/~Oz = - 138,000 + 29.8T(+300) cal= - 577,500 + 124.7T (• J (750 to 1536~A/IO2 = -144,600 + 33.45T(-300) cal = -605,100 + 140.0T(~-1250) J (1536 to 1700~At the oxygen potentials corresponding to Fe + FeCrzO a + Cr203 equilibria, the electronic contribution to the conductivity of ZrO2-CaO electrolyte was found to affect the measured emf. Application of a small 60 cycle A.C. voltage with an amplitude of 50 mv across the cell terminals reduced the time required to attain equilibrium at temperatures between 750 to 9500C by approximately a factor of two. The second law entropy of iron chromite obtained in this study is in good agreement with that calculated from thermal data. The entropies of formation of these spinel phases from the component oxides can be correlated to cation distribution and crystal field theory.

Uncertainty Quantification in Helicopter Performance Using Monte Carlo Simulations

The effect of structural and aerodynamic uncertainties on the performance predictions of a helicopter is investigated. An aerodynamic model based on blade element and momentum theory is used to predict the helicopter performance. The aeroelastic parameters, such as blade chord, rotor radius, two-dimensional lift-curve slope, blade profile drag coefficient, rotor angular velocity, blade pitch angle, and blade twist rate per radius of the rotor, are considered as random variables. The propagation of these uncertainties to the performance parameters, such as thrust coefficient and power coefficient, are studied using Monte Carlo Simulations. The simulations are performed with 100,000 samples of structural and aerodynamic uncertain variables with a coefficient of variation ranging from 1 to 5%. The scatter in power predictions in hover, axial climb, and forward flight for the untwisted and linearly twisted blades is studied. It is found that about 20-25% excess power can be required by the helicopter relative to the determination predictions due to uncertainties.

Refinement of thermodynamic properties of ReO2

The standard Gibbs energy of formation of ReO2 in the temperature range from 900 to 1200 K has been determined with high precision using a novel apparatus incorporating a buffer electrode between reference and working electrodes. The role of the buffer electrode was to absorb the electrochemical flux of oxygen through the solid electrolyte from the electrode with higher oxygen chemical potential to the electrode with lower oxygen potential. It prevented the polarization of the measuring electrode and ensured accurate data. The Re+ReO2 working electrode was placed in a closed stabilized-zirconia crucible to prevent continuous vaporization of Re2O7 at high temperatures. The standard Gibbs energy of the formation of ReO2 can be represented by the equation View the MathML source Accurate values of low and high temperature heat capacity of ReO2 are available in the literature. The thermal data are coupled with the standard Gibbs energy of formation, obtained in this study, to evaluate the standard enthalpy of formation of ReO2 at 298.15 K by the ‘third law’ method. The value of standard enthalpy of formation at 298.15 K is: View the MathML source(ReO2)/kJ mol−1=−445.1 (±0.2). The uncertainty estimate includes both random (2σ) and systematic errors.

Internal displacement reactions in multicomponent oxides: Part I. Line compounds with narrow homogeneity range

Structure and phase transition of LaO1−xF1+2x, prepared by solid-state reaction of La2O3 and LaF3, was investigated by X-ray powder diffraction and differential scanning calorimetry for both positive and negative values of the nonstoichiometric parameter x. The electrical conductivity was investigated as a function of temperature and oxygen partial pressure using AC impedance spectroscopy. Fluoride ion was identified as the migrating species in LaOF by coulometric titration and transport number determined by Tubandt technique and EMF measurements. Activation energy for conduction in LaOF was 58.5 (±0.8) kJ/mol. Conductivity increased with increasing fluorine concentration in the oxyfluoride phase, suggesting that interstitial fluoride ions are more mobile than vacancies. Although the values of ionic conductivity of cubic LaOF are lower, the oxygen partial pressure range for predominantly ionic conduction is larger than that for the commonly used stabilized-zirconia electrolytes. Thermodynamic analysis shows that the oxyfluoride is stable in atmospheres containing diatomic oxygen. However, the oxyfluoride phase can degrade with time at high temperatures in atmospheres containing water vapor, because of the higher stability of HF compared with H2O.

Prebreakdown Current and Sparking Potential in a Nonuniform Electric Field with a Crossed Magnetic Field

Prebreakdown currents in a coaxial cylindrical geometry in nitrogen have been measured with and without a crossed magnetic field. The range of parameters used in the investigation are 2.6 ÿ p ÿ 14.5 torr, 50 ÿ (E/p) ÿ 420 V cm-1 torr-1, and 43.0 ÿ H/p ÿ 1185 Oe torr-1 (p is the pressure, E is the electric field, and H is the magnetic field). The initial photoelectric current is obtained by allowing photons produced in an auxiliary glow discharge to strike the cathode. Ions and electrons produced in the auxiliary discharge are prevented from reaching the main gap by suitable shielding. By modifying the Rice equation for back diffusion, the measured ionization current multiplication without a crossed magnetic field is compared with the multiplication predicted by the Townsend growth equation for nonuniform electric fields. It is observed that over the range of 50 Ã�¿ (E/P)max Ã�¿ 250 [(E/P)max is the value of E/p at the central electrode of the coaxial system] measured and calculated multiplication of current agree with each other. With a crossed magnetic field the prebreakdown currents have been measured and compared with the theoretically calculated currents using the equivalent pressure concept. Agreement between the calculated and measured currents is not satisfactory, and this has been attributed more to the uncertainty in the collision frequency data available than nonuniformity of the electric field. Sparking potentials have been measured with and without a crossed magnetic field.

Dislocation mechanisms for plastic flow of nickel in the temperature range 4.2 – 1200 K

The temperature ranges of thermal and athermal deformation behaviour of nickel are identified by employing the temperature-dependence of flow-stress and strain-rate cycling data. The results are used to present a unified view of dislocation mechanisms of glide encompassing the two thermally activated and the intermediate athermal regimes of plastic flow.In the low-temperature thermally activated region (<250 K) the strain rate is found to be controlled by the repulsive intersection of glide and forest dislocations, in accordance with current ideas. The athermal stress in this region can be attributed mainly to the presence of strong attractive junctions which are overcome by means of Orowan bowing, a small contribution also coming from the elastic interactions between dislocations. The values of activation area and activation energy obtained in the high-temperature region (> 750 K) negate the operation of a diffusion-controlled mechanism. Instead, the data support a thermal activation model involving unzipping of the attractive junctions. The internal (long-range) stress contribution here results solely from the elastic interactions between dislocations. This view concerning the high-temperature plastic flow is further supported by the observation that the Cottrell–Stokes law is obeyed over large strains in the range 750–1200 K.

Representation of evidence: An approach to uncertainty handling in knowledge-based systems

Many knowledge based systems (KBS) transform a situation information into an appropriate decision using an in built knowledge base. As the knowledge in real world situation is often uncertain, the degree of truth of a proposition provides a measure of uncertainty in the underlying knowledge. This uncertainty can be evaluated by collecting `evidence' about the truth or falsehood of the proposition from multiple sources. In this paper we propose a simple framework for representing uncertainty in using the notion of an evidence space.

Sensitivity of nucleation phenomena on range of interaction potential

Theoretical and computational investigations of nucleation have been plagued by the sensitivity of the phase diagram to the range of the interaction potential. As the surface tension depends strongly on the range of interaction potential and as the classical nucleation theory (CNT) predicts the free energy barrier to be directly proportional to the cube of the surface tension, one expects a strong sensitivity of nucleation barrier to the range of the potential; however, CNT leaves many aspects unexplored. We find for gas-liquid nucleation in Lennard-Jones system that on increasing the range of interaction the kinetic spinodal (KS) (where the mechanism of nucleation changes from activated to barrierless) shifts deeper into the metastable region. Therefore the system remains metastable for larger value of supersaturation and this allows one to explore the high metastable region without encountering the KS. On increasing the range of interaction, both the critical cluster size and pre-critical minima in the free energy surface of kth largest cluster, at respective kinetic spinodals, shift towards smaller cluster size. In order to separate surface tension contribution to the increase in the barrier from other non-trivial factors, we introduce a new scaling form for surface tension and use it to capture both the temperature and the interaction range dependence of surface tension. Surprisingly, we find only a weak non-trivial contribution from other factors to the free energy barrier of nucleation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3685835]

Exact entanglement studies of strongly correlated systems: role of long-range interactions and symmetries of the system

We study the bipartite entanglement of strongly correlated systems using exact diagonalization techniques. In particular, we examine how the entanglement changes in the presence of long-range interactions by studying the Pariser-Parr-Pople model with long-range interactions. We compare the results for this model with those obtained for the Hubbard and Heisenberg models with short-range interactions. This study helps us to understand why the density matrix renormalization group (DMRG) technique is so successful even in the presence of long-range interactions. To better understand the behavior of long-range interactions and why the DMRG works well with it, we study the entanglement spectrum of the ground state and a few excited states of finite chains. We also investigate if the symmetry properties of a state vector have any significance in relation to its entanglement. Finally, we make an interesting observation on the entanglement profiles of different states (across the energy spectrum) in comparison with the corresponding profile of the density of states. We use isotropic chains and a molecule with non-Abelian symmetry for these numerical investigations.

Measurement and Applications of Long-Range Heteronuclear Scalar Couplings: Recent Experimental and Theoretical Developments

The use of long-range heteronuclear couplings, in association with 1H1H scalar couplings and NOE restraints, has acquired growing importance for the determination of the relative stereochemistry, and structural and conformational information of organic and biological molecules. However, the routine use of such couplings is hindered by the inherent difficulties in their measurement. Prior to the advancement in experimental techniques, both long-range homo- and heteronuclear scalar couplings were not easily accessible, especially for very large molecules. The development of a large number of multidimensional NMR experimental methodologies has alleviated the complications associated with the measurement of couplings of smaller strengths. Subsequent application of these methods and the utilization of determined J-couplings for structure calculations have revolutionized this area of research. Problems in organic, inorganic and biophysical chemistry have also been solved by utilizing the short- and long-range heteronuclear couplings. In this minireview, we discuss the advantages and limitations of a number of experimental techniques reported in recent times for the measurement of long-range heteronuclear couplings and a few selected applications of such couplings. This includes the study of medium- to larger-sized molecules in a variety of applications, especially in the study of hydrogen bonding in biological systems. The utilization of these couplings in conjunction with theoretical calculations to arrive at conclusions on the hyperconjugation, configurational analysis and the effect of the electronegativity of the substituents is also discussed.

Microelectromechanical torsional varactors with low parasitic capacitances and high dynamic range

This work focuses on the design of torsional microelectromechanical systems (MEMS) varactors to achieve highdynamic range of capacitances. MEMS varactors fabricated through the polyMUMPS process are characterized at low and high frequencies for their capacitance-voltage characteristics and electrical parasitics. The effect of parasitic capacitances on tuning ratio is studied and an equivalent circuit is developed. Two variants of torsional varactors that help to improve the dynamic range of torsional varactors despite the parasitics are proposed and characterized. A tuning ratio of 1:8, which is the highest reported in literature, has been obtained. We also demonstrate through simulations that much higher tuning ratios can be obtained with the designs proposed. The designs and experimental results presented are relevant to CMOS fabrication processes that use low resistivity substrate. (C) 2012 Society of Photo-Optical Instrumentation Engineers (SPIE). DOI: 10.1117/1.JMM.11.1.013006]