System Nd-Pd-O: Phase diagram and thermodynamic properties of oxides using a solid-state cell with advanced features

An isothermal section of the phase diagram for the system Nd-Pd-O at 1350 K has been established by equilibration of samples representing 13 different compositions and phase identification after quenching by optical and scanning electron microscopy, x-ray diffraction, and energy dispersive analysis of x-rays. The binary oxides PdO and NdO were not stable at 1350 K. Two ternary oxides Nd4PdO7 and Nd2Pd2O5 were identified. Solid and liquid alloys, as well as the intermetallics NdPd3 and NdPd5, were found to be in equilibrium with Nd2O3. Based on the phase relations, three solidstate cells were designed to measure the Gibbs energies of formation of PdO and the two ternary oxides. An advanced version of the solid-state cell incorporating a buffer electrode was used for high-temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MP a as the reference electrode. Electromotive force measurements, conducted from 950 to 1425 K, indicated the presence of a third ternary oxide Nd2PdO4, stable below 1135 (±10) K. Additional cells were designed to study this compound. The standard Gibbs energy of formation of PdO (†f G 0) was measured from 775 to 1125 Kusing two separate cell designs against the primary reference standard for oxygen chemical potential. Based on the thermodynamic information, chemical potential diagrams for the system Nd-Pd-O were also developed.

An advanced design of the solid-state cell for accurate thermodynamic measurements on ternary oxides: system Sm–Pd–O

An advanced design of the solid-state cell incorporating a buffer electrode has been developed for high temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. The application of the novel design and its advantages have been demonstrated by measuring the standard Gibbs energies of formation of ternary oxides of the system Sm–Pd–O. Yttria-stabilized zirconia was 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 Sm–Pd–O were investigated at 1273 K. The two ternary oxides, Sm4PdO7 and Sm2Pd2O5, compositions of which fall on the Sm2O3–PdO join, were found to coexist with pure metal Pd. The thermodynamic properties of the ternary oxides were measured using three-phase electrodes in the temperature range 950–1425 K. During electrochemical measurements a third ternary oxide, Sm2PdO4, was found to be stable at low temperature. The standard Gibbs energies of formation (Δf(ox)Go) of the compounds from their component binary oxides Sm2O3 and PdO, can be represented by the equations: Sm4PdO7: Δf(ox)Go (J mol−1)=−34,220+0.84T(K) (±280); Sm2PdO4: Δf(ox)Go (J mol−1)=−33,350+2.49T(K) (±230); Sm2Pd2O5: Δf(ox)Go (J mol−1)=−59,955+1.80T(K) (±320). Based on the thermodynamic information, three-dimensional P–T–C and chemical potential diagrams for the system Sm–Pd–O were developed.

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.

Full spin and spatial symmetry adapted technique for correlated electronic hamiltonians: Application to an icosahedral cluster

One of the long standing problems in quantum chemistry had been the inability to exploit full spatial and spin symmetry of an electronic Hamiltonian belonging to a non-Abelian point group. Here, we present a general technique which can utilize all the symmetries of an electronic (magnetic) Hamiltonian to obtain its full eigenvalue spectrum. This is a hybrid method based on Valence Bond basis and the basis of constant z-component of the total spin. This technique is applicable to systems with any point group symmetry and is easy to implement on a computer. We illustrate the power of the method by applying it to a model icosahedral half-filled electronic system. This model spans a huge Hilbert space (dimension 1,778,966) and in the largest non-Abelian point group. The C60 molecule has this symmetry and hence our calculation throw light on the higher energy excited states of the bucky ball. This method can also be utilized to study finite temperature properties of strongly correlated systems within an exact diagonalization approach. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012

Influence of Bottom Bubbling Rate on Formation of Metal Emulsion in Al-Cu Alloy and Molten Salt System

In steel refining process, an increase of interfacial area between the metal and slag through the metal droplets emulsified into the slag, so-called ``metal emulsion'', is one prevailing view for improving the reaction rate. The formation of metal emulsion was experimentally evaluated using Al-Cu alloy as metal phase and chloride salt as slag phase under the bottom bubbling condition. Samples were collected from the center of the salt phase in the container. Large number of metal droplets were separated from the salt by dissolving it into water. The number, surface area, and weight of the droplets increased with the gas flow rate and have local maximum values. The formation and sedimentation rates of metal droplets were estimated using a mathematical model. The formation rate increased with the gas flow rate and has a local maximum value as a function of gas flow rate, while the sedimentation rate is independent of the gas flow rate under the bottom bubbling condition. Three types of formation mode of metal emulsion, which occurred by the rupture of metal film around the bubble, were observed using high speed camera. During the process, an elongated column covered with metal film was observed with the increasing gas flow rate. This elongated column sometimes reached to the top surface of the salt phase. In this case, it is considered that fine droplets were not formed and in consequence, the weight of metal emulsion decreased at higher gas flow rate.

A scalable network port scan detection system on FPGA

With ever increasing network speed, scalable and reliable detection of network port scans has become a major challenge. In this paper, we present a scalable and flexible architecture and a novel algorithm, to detect and block port scans in real time. The proposed architecture detects fast scanners as well as stealth scanners having large inter-probe periods. FPGA implementation of the proposed system gives an average throughput of 2 Gbps with a system clock frequency of 100 MHz on Xilinx Virtex-II Pro FPGA. Experimental results on real network trace show the effectiveness of the proposed system in detecting and blocking network scans with very low false positives and false negatives.

A Hybrid Multilevel Inverter System Based on Dodecagonal Space Vectors for Medium Voltage IM Drives

Dodecagonal (12-sided) space vector pulsewidth modulation (PWM) schemes are characterized by the complete absence of (6n +/- 1)th-order harmonics (for odd n) in the phase voltages, within the linear modulation range and beyond, including over-modulation. This paper presents a new topology suitable for the realization of such multilevel inverter schemes for induction motor (IM) drives, by cascading two-level inverters with flying-capacitor-inverter fed floating H-bridge cells. Now, any standard IM may be used to get the dodecagonal operation which hitherto was possible only with open-end winding IM. To minimize the current total harmonic distortion (THD), a strategy for synchronous PWM is also proposed. It is shown that the proposed method is capable of obtaining better THD figures, compared to conventional dodecagonal schemes. The topology and the PWM strategy are validated through analysis and subsequently verified experimentally.

A nine-level inverter topology for medium-voltage induction motor drive with open-end stator winding

A new scheme for nine-level voltage space-vector generation for medium-voltage induction motor (IM) drives with open-end stator winding is presented in this paper. The proposed nine-level power converter topology consists of two conventional three-phase two-level voltage source inverters powered by isolated dc sources and six floating-capacitor-connected H-bridges. The H-bridge capacitor voltages are effectively maintained at the required asymmetrical levels by employing a space vector modulation (SVPWM) based control strategy. An interesting feature of this topology is its ability to function in five-or three-level mode, in the entire modulation range, at full-power rating, in the event of any failure in the H-bridges. This feature significantly improves the reliability of the proposed drive system. Each leg of the three-phase two-level inverters used in this topology switches only for a half cycle of the reference voltage waveform. Hence, the effective switching frequency is reduced by half, resulting in switching loss reduction in high-voltage devices. The transient as well as the steady-state performance of the proposed nine-level inverter-fed IM drive system is experimentally verified in the entire modulation range including the overmodulation region.

e-SURAKSHAK: A Cyber-Physical Healthcare System with Service Oriented Architecture

In this paper we present the design of ``e-SURAKSHAK,'' a novel cyber-physical health care management system of Wireless Embedded Internet Devices (WEIDs) that sense vital health parameters. The system is capable of sensing body temperature, heart rate, oxygen saturation level and also allows noninvasive blood pressure (NIBP) measurement. End to end internet connectivity is provided by using 6LoWPAN based wireless network that uses the 802.15.4 radio. A service oriented architecture (SOA) 1] is implemented to extract meaningful information and present it in an easy-to-understand form to the end-user instead of raw data made available by sensors. A central electronic database and health care management software are developed. Vital health parameters are measured and stored periodically in the database. Further, support for real-time measurement of health parameters is provided through a web based GUI. The system has been implemented completely and demonstrated with multiple users and multiple WEIDs.

System-level SoC near-field (NF) emissions: Simulation to measurement correlation

As System-on-Chip (SoC) designs migrate to 28nm process node and beyond, the electromagnetic (EM) co-interactions of the Chip-Package-Printed Circuit Board (PCB) becomes critical and require accurate and efficient characterization and verification. In this paper a fast, scalable, and parallelized boundary element based integral EM solutions to Maxwell equations is presented. The accuracy of the full-wave formulation, for complete EM characterization, has been validated on both canonical structures and real-world 3-D system (viz. Chip + Package + PCB). Good correlation between numerical simulation and measurement has been achieved. A few examples of the applicability of the formulation to high speed digital and analog serial interfaces on a 45nm SoC are also presented.

A context aware collaborative service provisioning system for mobile-commerce

In the process of service provisioning, providing required service to the user without user intervention, with reduction of the cognitive over loading is a real challenge. In this paper we propose a user centred context aware collaborative service provisioning system, which make use of context along with collaboration to provide the required service to the user dynamically. The system uses a novel approach of query expansion along with interactive and rating matrix based collaboration. Performance of the system is evaluated in Mobile-Commerce environment. The results show that the system is time efficient and perform with better precision and recall in comparison with context aware system.

Magnetoresistance and electroresistance effects in Fe3O4 nanoparticle system

Nearly monodisperse spherical magnetite (Fe3O4) nanoparticles are prepared by colloidal chemistry route. Magnetic and electronic transport properties of the annealed pellets of these nanoparticles are reported. Effect of external magnetic and electric fields on the magnetic and transport properties of the material are studied as a function of temperature. We find that the highest resistance state of the ferromagnetic system occurs at a magnetic field which is approximately equal to its magnetic coercivity; this establishes the magnetoresistance (MR) in this system to be of the conventional tunnelling type MR as against the spin-valve type MR found more recently in some ferromagnetic oxide systems. The material also shows electroresistance (ER) property with its low-temperature resistance being strongly dependent on the excitation current that is used for the measurement. This ER effect is concluded to be intrinsic to the material and is attributed to the electric field-induced melting of the charge-order state in magnetite.

Valence band electronic structure of Nd1-xYxMnO3 using X-ray absorption, photoemission and GGA plus U calculations

The electronic structures of Nd1-xYxMnO3 (x=0-0.5) were studied using X-ray absorption near-edge structure (XANES) at the Mn L-3,L-2- and O K-edge along with valence-band photoemission spectroscopy (VB-PES). The systematic increase in white-line intensity of the Mn L-3,L-2-edge with doping, suggests a decrease in the occupancy of Mn 3d orbitals. The O K-edge XANES shows a depletion of unoccupied states above the Fermi energy. The changes in the O K-edge spectra due to doping reflects an increase in the Jahn-Teller distortion. The VB-PES shows broadening of the features associated with Mn 3d and O 2p hybridized states and the shift of these features to a slightly higher binding energy in agreement with our GGA + U calculations. The system shows a net shift of the occupied and unoccupied states away from the Fermi energy with doping. The shift in theoretical site-projected density of states of x=0.5 composition with respect to x=0 suggest a subtle change from a charge transfer to Mott-Hubbard type insulator. (C) 2013 Elsevier B.V. All rights reserved.

Electronic band Structure and Photoemission Spectra of Graphene on Silicon Substrate

Synergizing graphene on silicon based nanostructures is pivotal in advancing nano-electronic device technology. A combination of molecular dynamics and density functional theory has been used to predict the electronic energy band structure and photo-emission spectrum for graphene-Si system with silicon as a substrate for graphene. The equilibrium geometry of the system after energy minimization is obtained from molecular dynamics simulations. For the stable geometry obtained, density functional theory calculations are employed to determine the energy band structure and dielectric constant of the system. Further the work function of the system which is a direct consequence of photoemission spectrum is calculated from the energy band structure using random phase approximations.