Solid-state cells with buffer electrodes for accurate thermodynamic measurements: system Nd-Ir-O

A new design for the solid-state cell incorporating a buffer electrode for high-temperature thermodynamic measurements is presented. The function of the buffer electrode, placed between the reference and working electrodes, is to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevents polarization of the measuring electrode and ensures accurate data. The application of this novel design and its advantages are demonstrated by measurement of the standard Gibbs energies of formation of Nd6Ir2O13 (low-temperature form) and Nd2Ir2O7 in the temperature range from 975 to 1450 K. Yttria-stabilized zirconia is used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode. For the design of appropriate working electrodes, phase relations in the ternary system NdIrO were investigated at 1350 K. The two ternary oxides, Nd6Ir2O13 and Nd2Ir2O7, compositions of which fall on the join Nd2O3IrO2, were found to coexist with pure metal Ir. Therefore, two working electrodes were prepared consisting of mixtures of Ir+Nd2O3+Nd6Ir2O13 and Ir+Nd6Ir2O13+ Nd2Ir2O7. These mixtures unambiguously define unique oxygen chemical potentials under isothermal and isobaric conditions. The standard Gibbs energies of formation (ΔG°f (ox)) of the compounds from their component binary oxides Nd2O3 and IrO2, obtained from the emf of the cells, can be represented by the equations:View the MathML source View the MathML source Based on the thermodynamic information, chemical potential diagrams for the system NdIrO are developed.

Nonlinear dynamic state estimation in instrumented structures with conditionally linear Gaussian substructures

Many problems of state estimation in structural dynamics permit a partitioning of system states into nonlinear and conditionally linear substructures. This enables a part of the problem to be solved exactly, using the Kalman filter, and the remainder using Monte Carlo simulations. The present study develops an algorithm that combines sequential importance sampling based particle filtering with Kalman filtering to a fairly general form of process equations and demonstrates the application of a substructuring scheme to problems of hidden state estimation in structures with local nonlinearities, response sensitivity model updating in nonlinear systems, and characterization of residual displacements in instrumented inelastic structures. The paper also theoretically demonstrates that the sampling variance associated with the substructuring scheme used does not exceed the sampling variance corresponding to the Monte Carlo filtering without substructuring. (C) 2012 Elsevier Ltd. All rights reserved.

Linear programming approach for state estimation incorporating phasor measurements

This paper presents methodologies for incorporating phasor measurements into conventional state estimator. The angle measurements obtained from Phasor Measurement Units are handled as angle difference measurements rather than incorporating the angle measurements directly. Handling in such a manner overcomes the problems arising due to the choice of reference bus. Current measurements obtained from Phasor Measurement Units are treated as equivalent pseudo-voltage measurements at the neighboring buses. Two solution approaches namely normal equations approach and linear programming approach are presented to show how the Phasor Measurement Unit measurements can be handled. Comparative evaluation of both the approaches is also presented. Test results on IEEE 14 bus system are presented to validate both the approaches.

Dynamic state estimation for identifying earthquake support motions in instrumented structures

The problem of identification of multi-component and (or) spatially varying earthquake support motions based on measured responses in instrumented structures is considered. The governing equations of motion are cast in the state space form and a time domain solution to the input identification problem is developed based on the Kalman and particle filtering methods. The method allows for noise in measured responses, imperfections in mathematical model for the structure, and possible nonlinear behavior of the structure. The unknown support motions are treated as hypothetical additional system states and a prior model for these motions are taken to be given in terms of white noise processes. For linear systems, the solution is developed within the Kalman filtering framework while, for nonlinear systems, the Monte Carlo simulation based particle filtering tools are employed. In the latter case, the question of controlling sampling variance based on the idea of Rao-Blackwellization is also explored. Illustrative examples include identification of multi-component and spatially varying support motions in linear/nonlinear structures.

Globally coupled stochastic two-state oscillators: Fluctuations due to finite numbers

Infinite arrays of coupled two-state stochastic oscillators exhibit well-defined steady states. We study the fluctuations that occur when the number N of oscillators in the array is finite. We choose a particular form of global coupling that in the infinite array leads to a pitchfork bifurcation from a monostable to a bistable steady state, the latter with two equally probable stationary states. The control parameter for this bifurcation is the coupling strength. In finite arrays these states become metastable: The fluctuations lead to distributions around the most probable states, with one maximum in the monostable regime and two maxima in the bistable regime. In the latter regime, the fluctuations lead to transitions between the two peak regions of the distribution. Also, we find that the fluctuations break the symmetry in the bimodal regime, that is, one metastable state becomes more probable than the other, increasingly so with increasing array size. To arrive at these results, we start from microscopic dynamical evolution equations from which we derive a Langevin equation that exhibits an interesting multiplicative noise structure. We also present a master equation description of the dynamics. Both of these equations lead to the same Fokker-Planck equation, the master equation via a 1/N expansion and the Langevin equation via standard methods of Ito calculus for multiplicative noise. From the Fokker-Planck equation we obtain an effective potential that reflects the transition from the monomodal to the bimodal distribution as a function of a control parameter. We present a variety of numerical and analytic results that illustrate the strong effects of the fluctuations. We also show that the limits N -> infinity and t -> infinity(t is the time) do not commute. In fact, the two orders of implementation lead to drastically different results.

Dynamic Site Characterization and Correlation of Shear Wave Velocity with Standard Penetration Test `N' Values for the City of Agartala, Tripura State, India

Seismic site characterization is the basic requirement for seismic microzonation and site response studies of an area. Site characterization helps to gauge the average dynamic properties of soil deposits and thus helps to evaluate the surface level response. This paper presents a seismic site characterization of Agartala city, the capital of Tripura state, in the northeast of India. Seismically, Agartala city is situated in the Bengal Basin zone which is classified as a highly active seismic zone, assigned by Indian seismic code BIS-1893, Indian Standard Criteria for Earthquake Resistant Design of Structures, Part-1 General Provisions and Buildings. According to the Bureau of Indian Standards, New Delhi (2002), it is the highest seismic level (zone-V) in the country. The city is very close to the Sylhet fault (Bangladesh) where two major earthquakes (M (w) > 7) have occurred in the past and affected severely this city and the whole of northeast India. In order to perform site response evaluation, a series of geophysical tests at 27 locations were conducted using the multichannel analysis of surface waves (MASW) technique, which is an advanced method for obtaining shear wave velocity (V (s)) profiles from in situ measurements. Similarly, standard penetration test (SPT-N) bore log data sets have been obtained from the Urban Development Department, Govt. of Tripura. In the collected data sets, out of 50 bore logs, 27 were selected which are close to the MASW test locations and used for further study. Both the data sets (V (s) profiles with depth and SPT-N bore log profiles) have been used to calculate the average shear wave velocity (V (s)30) and average SPT-N values for the upper 30 m depth of the subsurface soil profiles. These were used for site classification of the study area recommended by the National Earthquake Hazard Reduction Program (NEHRP) manual. The average V (s)30 and SPT-N classified the study area as seismic site class D and E categories, indicating that the city is susceptible to site effects and liquefaction. Further, the different data set combinations between V (s) and SPT-N (corrected and uncorrected) values have been used to develop site-specific correlation equations by statistical regression, as `V (s)' is a function of SPT-N value (corrected and uncorrected), considered with or without depth. However, after considering the data set pairs, a probabilistic approach has also been presented to develop a correlation using a quantile-quantile (Q-Q) plot. A comparison has also been made with the well known published correlations (for all soils) available in the literature. The present correlations closely agree with the other equations, but, comparatively, the correlation of shear wave velocity with the variation of depth and uncorrected SPT-N values provides a more suitable predicting model. Also the Q-Q plot agrees with all the other equations. In the absence of in situ measurements, the present correlations could be used to measure V (s) profiles of the study area for site response studies.

Reservoir Operation with Fuzzy State Variables for Irrigation of Multiple Crops

This paper presents the development and application of a stochastic dynamic programming model with fuzzy state variables for irrigation of multiple crops. A fuzzy stochastic dynamic programming (FSDP) model is developed in which the reservoir storage and soil moisture of the crops are considered as fuzzy numbers, and the reservoir inflow is considered as a stochastic variable. The model is formulated with an objective of minimizing crop yield deficits, resulting in optimal water allocations to the crops by maintaining storage continuity and soil moisture balance. The standard fuzzy arithmetic method is used to solve all arithmetic equations with fuzzy numbers, and the fuzzy ranking method is used to compare two or more fuzzy numbers. The reservoir operation model is integrated with a daily-based water allocation model, which results in daily temporal variations of allocated water, soil moisture, and crop deficits. A case study of an existing Bhadra reservoir in Karnataka, India, is chosen for the model application. The FSDP is a more realistic model because it considers the uncertainty in discretization of state variables. The results obtained using the FSDP model are found to be more acceptable for the case study than those of the classical stochastic dynamic model and the standard operating model, in terms of 10-day releases from the reservoir and evapotranspiration deficit. (C) 2015 American Society of Civil Engineers.

Fuzzy State Real-Time Reservoir Operation Model for Irrigation with Gridded Rainfall Forecasts

A short-term real-time operation model with fuzzy state variables is developed for irrigation of multiple crops based on earlier work on long-term steady-state policy. The features of the model that distinguish it from the earlier work are (1) apart from inclusion of fuzziness in reservoir storage and in soil moisture of crops, spatial variations in rainfall and soil moisture of crops are included in the real-time operation model by considering gridded command area with a grid size of 0.5 degrees latitude by 0.5 degrees longitude; (2) the water allocation model and soil moisture balance equations are integrated with the real-time operation model with consideration of ponding water depth for Paddy crop; the model solution specifies reservoir releases for irrigation in a 10-day time period and allocations among the crops on a daily basis at each grid by maintaining soil moisture balance at the end of the day; and (3) the release policy is developed using forecasted daily rainfall data of each grid and is implemented for the current time period using actual 10-day inflow and actual daily rainfall of each grid. The real-time operation model is applied to Bhadra Reservoir in Karnataka, India. The results obtained using the real-time operation model are compared with those of the standard operating policy model. Inclusion of fuzziness in reservoir storage and soil moisture of crops captures hydrologic uncertainties in real time. Considerations of irrigation decisions on a daily basis and the gridded command area result in variations in allocating water to the crops, variations in actual crop evapotranspiration, and variations in soil moisture of the crops on a daily basis for each grid of the command area. (C) 2015 American Society of Civil Engineers.

Electromechanical analysis of piezoelectric bimorph actuator in static state considering the nonlinearity at high electric field

This article contains electromechanical analysis of a piezoelectric bimorph actuator at high electric field by incorporating second-order constitutive equations of piezoelectric material. Tip deflection, block force, block moment, block load, output strain energy, output energy density, input electrical energy, and energy efficiency are analytically derived for the actuator at high electric field. The analysis shows that output energy and energy density increase more rapidly at high electric field, compared to the prediction by the linear model. The analysis shows energy efficiency depends on electric field. Some analytical results are validated with the published experimental results.

SecB binds only to a late native-like intermediate in the folding pathway of barstar and not to the unfolded state

SecB is a cytosolic, tetrameric chaperone of Escherichia coli which maintains precursor proteins in a translocation competent state. We have investigated the effect of SecB on the refolding kinetics of the small protein barstar in I M guanidine hydrochloride at pH 7.0 and 25 degrees C using fluorescence spectroscopy. We show that SecB does not bind either the native or the unfolded states of barstar but binds to a late near-native intermediate along the folding pathway. For barstar, polypeptide collapse and formation of a hydrophobic surface are required for binding to SecB. SecB does not change the apparent rate constant of barstar refolding. The kinetic data for SecB binding to barstar are not consistent with simple kinetic partitioning models.

Electronic Properties of the Vortex State in Cuprate Superconductors

The superconducting state of the cuprates in the presence of a magnetic field has been investigated very actively in the past few years through measurements of electrical and thermal transport, ac conductivity, specific heat, and other quantities. The observed behavior is not well understood; it probes the nature of quasiparticies, vortices, and their interactions in a superconductor with nodes in the pair amplitude. We summarize here experimental results and our attempts to understand the phenomena.

Sizable photocurrent and emission from solid state devices based on CdS nanoparticles

CdS nanoparticles exhibit size dependent optical and electrical properties. We report here the photocurrent and I-V characteristic studies of CdS nanoparticle devices. A sizable short circuit photocurrent was observed in the detection range governed by the size of the clusters. We speculate on the mechanisms leading to the photocurrent and emission in these nanometer scale systems.

Exact N-wave solutions of generalized Burgers equations

Exact N-wave solutions for the generalized Burgers equation u(t) + u(n)u(x) + (j/2t + alpha) u + (beta + gamma/x) u(n+1) = delta/2u(xx),where j, alpha, beta, and gamma are nonnegative constants and n is a positive integer, are obtained. These solutions are asymptotic to the (linear) old-age solution for large time and extend the validity of the latter so as to cover the entire time regime starting where the originally sharp shock has become sufficiently thick and the viscous effects are felt in the entire N wave.

Stress-state permeability relationships for clays with coarse fraction

In standard laboratory consolidation tests, only the fraction of soil passing through a particular size of the sieve, called the matrix material, is used. This size is usually restricted to 1/10 of the height of the consolidation ring. Particles larger than this size that are removed before the test may consist of gravel, fragments of rock, or other coarse materials. Hence, it is not possible to estimate the compressibility and permeability of the total material based on the compressibility and permeability behavior obtained from laboratory consolidation tests on the matrix material. In the present investigation an attempt has been made to estimate the compressibility and permeability behavior of the total material based on the compressibility and permeability behavior of the matrix material. The results indicate that the presence of coarse particles will reduce the compressibility of the soil in proportion to the coarse fraction present in the whole soil and will not affect the permeability of the soil for the range investigated. If the coarse fraction exceeds the Limiting percentage, the void ratio-vertical effective stress path will also start to deviate from the predicted path. An expression has been developed to estimate approximately the deviating pressure, and it is found to depend on the soil type as well as the percent clay fraction.

Ergodic control of partially observed Markov chains

The ergodic or long-run average cost control problem for a partially observed finite-state Markov chain is studied via the associated fully observed separated control problem for the nonlinear filter. Dynamic programming equations for the latter are derived, leading to existence and characterization of optimal stationary policies.