Computational Analysis of Flow through a Multiple Nozzle Driven Laser Cavity and Diffuser

Computations have been carried out for simulating supersonic flow through a set of converging-diverging nozzles with their expanding jets forming a laser cavity and flow patterns through diffusers, past the cavity. A thorough numerical investigation with 3-D RANS code is carried out to capture the flow distribution which comprises of shock patterns and multiple supersonic jet interactions. The analysis of pressure recovery characteristics during the flow through the diffusers is an important parameter of the simulation and is critical for the performance of the laser device. The results of the computation have shown a close agreement with the experimentally measured parameters as well as other established results indicating that the flow analysis done is found to be satisfactory.

Docking and free energy simulations to predict conformational domains involved in hCG-LH receptor interactions using recombinant antibodies

Single chain fragment variables (ScFvs) have been extensively employed in studying the protein-protein interactions. ScFvs derived from phage display libraries have an additional advantage of being generated against a native antigen, circumventing loss of information on conformational epitopes. In the present study, an attempt has been made to elucidate human chorionic gonadotropin (hCG)-luteinizing hormone (LH) receptor interactions by using a neutral and two inhibitory ScFvs against hCG. The objective was to dock a computationally derived model of these ScFvs onto the crystal structure of hCG and understand the differential roles of the mapped epitopes in hCG-LH receptor interactions. An anti-hCG ScFv, whose epitope was mapped previously using biochemical tools, served as the positive control for assessing the quality of docking analysis. To evaluate the role of specific side chains at the hCG-ScFv interface, binding free energy as well as residue interaction energies of complexes in solution were calculated using molecular mechanics Poisson-Boltzmann/surface area method after performing the molecular dynamic simulations on the selected hCG-ScFv models and validated using biochemical and SPR analysis. The robustness of these calculations was demonstrated by comparing the theoretically determined binding energies with the experimentally obtained kinetic parameters for hCG-ScFv complexes. Superimposition of hCG-ScFv model onto a model of hCG complexed with the 51-266 residues of LH receptor revealed importance of the residues previously thought to be unimportant for hormone binding and response. This analysis provides an alternate tool for understanding the structure-function analysis of ligand-receptor interactions. Proteins 2011;79:3108-3122. (C) 2011 Wiley-Liss, Inc.

Wear behavior of plasma electrolytic oxidation (PEO) and hybrid coatings of PEO and laser on MRI 230D magnesium alloy

Wear resistant coatings were produced on a permanent mould cast MRI 230D Mg alloy by (a) PEO in silicate based electrolyte, (b) PEO in phosphate based electrolyte, (c) hybrid coatings of silicate PEO followed by laser surface alloying (LSA) with Al and Al(2)O(3), and (d) hybrid coatings of phosphate PEO followed by LSA with Al and Al(2)O(3). Microstructural characterization of the coatings was carried out by scanning electron microscopy (SEM) and X(ray diffraction. The tribological behavior of the coatings was investigated under dry sliding condition using linearly reciprocating ball-on-flat wear test. Both the PEO coatings exhibited a friction coefficient of about 0.8 and hybrid coatings exhibited a value of about 0.5 against the AISI 52100 steel ball as the friction partner, which were slightly reduced with the increase in applied load. The PEO coatings sustained the test without failure at 2 N load but failed at 5 N load due to micro-fracture caused by high contact stresses. The hybrid coatings did not get completely worn off at 2 N load but were completely removed exposing the substrate at 5 N load. The PEO coatings exhibited better wear resistance than the hybrid coatings and silicate PEO coatings exhibited better wear resistance than the phosphate PEO coatings. Both the PEO coatings melted/decomposed on laser irradiation and all the hybrid coatings exhibited similar microstructure and wear behavior irrespective of the nature of the primary PEO coating or laser energies. SEM examination of worn surfaces indicated abrasive wear combined with adhesive wear for all the specimens. The surface of the ball exhibited a discontinuous transfer layer after the wear test. (C) 2011 Elsevier B.V. All rights reserved.

Gibbs free energies of formation of ZnAl2O4 and ZnCr2O4

The standard free energies of formation of zinc aluminate and chromite were determined by measuring the oxygen potential over a solid CuZn alloy, containing 10 at.−% Zn, in equilibrium with ZnO, ZnAl2O4+Al2O3(χ) and ZnCr2O4+Cr2O3, in the temperature range 700–900°C. The oxygen potential was monitored by means of a solid oxide galvanic cell in which a Y2O3 ThO2 pellet was sandwiched between a CaOZrO2 crucible and tube. The temperature dependence of the free energies of formation of the interoxidic compounds can be represented by the equations, The heat of formation of the spinels calculated from the measurements by the “Second Law method” is found to be in good agreement with calorimetrically determined values. Using an empirical correlation for the entropy of formation of cubic spinel phases from oxides with rock-salt and corundum structures and the measured high temperature cation distribution in ZnAl2O4, the entropy of transformation of ZnO from wurtzite to rock-salt structure is evaluated.

Potentiometric determination of the Gibbs free energy of formation of cadmium and magnesium chromites

The standard Gibbs free energy of formation of magnesium and cadmiumchromites have been determined by potentiometric measurements on reversiblesolid-state electrochemical cells [dformula (Au-5%Cd, , Au-5%Cd; Pt, + , CaO-ZrO[sub 2], + ,Pt; CdO, , CdCr[sub 2]O[sub 4] + Cr[sub 2]O[sub 3])] in the temperature range 500°–730°C, and [dformula Pt, Cr + Cr[sub 2]O[sub 3]/Y[sub 2]O[sub 3]-ThO[sub 2]/Cr + MgCr[sub 2]O[sub 4] + MgO, Pt] in the temperature range 800°–1200°C. The temperature dependence of the freeenergies of formation of the ternary compounds can be represented by theequations [dformula CdO(r.s.) + Cr[sub 2]O[sub 3](cor) --> CdCr[sub 2]O[sub 4](sp)] [dformula Delta G[sup 0] = - 42,260 + 7.53T ([plus-minus]400) J] and [dformula MgO(r.s.) + Cr[sub 2]O[sub 3](cor) --> MgCr[sub 2]O[sub 4](sp)] [dformula Delta G[sup 0] = - 45,200 + 5.36T ([plus-minus]400) J] The entropies of formation of these spinels are discussed in terms of cationdisorder and extent of reduction of Cr3+ ions to Cr2+ ions. Thermodynamicdata on the chromates of cadmium and magnesium are derived by combiningthe results obtained in this study with information available in the literatureon high temperature, high pressure phase equilibria in the systems CdO-Cr2O3-O2 and MgO-Cr2O3-O2.

Gibbs free energy of formation of magnesium stannate

he thermodynamic properties of the spinel Mg2SnO4 have been determined by emf measurements on the solid oxide galvanic cell,View the MathML source in the temperature range 600 to 1000°C. The Gibbs' free energy of formation of Mg2SnO4 from the component oxides can be expressed as View the MathML source,View the MathML source These values are in good agreement with the information obtained by Jackson et al. [Earth Planet. Sci. Lett.24, 203 (1974)] on the high pressure decomposition of magnesium stannate into component oxides at different temperatures. The thermodynamic data suggest that the spinel phase is entropy stabilized, and would be unstable below 207 (±25)°C at atmospheric pressure. Based on the information obtained in this study and trends in the stability of aluminate and chromite spinels, it can be deduced that the stannates of nickel and copper(II) are unstable.

Gibbs free energies of formation of indium (III) oxide and sulphate

Emf measurements on the galvanic cell Pt, Ta, In + In,O, / Tho,-Y,03 / Cu + C+O, Pt were used to obtain the standard free energy of formation of 1%03fr om 600 to 900°C. Differential thermal analysis was used to detect the decomposition of In2(S0,), under controlled SO2 + O2 + Ar mixtures in thqtemperature range 640-8wC. X-ray diffraction analysis indicated that the decomposition product was 1%03 without an oxywlphate intermediate. The following equations were obtained for the variation of the standard free-energy change(Jlmole) with temperature:

Highly efficient dialkylphosphate-mediated syntheses of hydantoins and a bicyclohydantoin under solvent-free conditions

Diversely substituted hydantoins have been synthesized by new strategy from cyanamide based precursor, that is, methyl N-cyano-N-alkyl/arylaminoacetate. Dialkylphosphates were employed as the mild reagent to hydrolyze and cyclize the substrate in one step to give quantitative yields of the desired products. Syntheses of multivalent hydantoins viz bis-hydantoin, bicyclohydantoin have potentially widened the scope and applicability of the present method. Solvent-free conditions and very easy work-up procedure make the reaction convenient and eco-friendly. Single crystal structures of some of the representative compounds are also reported. (C) 2011 Elsevier Ltd. All rights reserved.

Gibbs’ free energies of formation of Cu2Ln2O5 (Ln = Tb, Dy, Er, Yb) compounds

The standard Gibbs' free energies of formation of compounds of type Cu2L%05 (Ln = Tb,Dy,Er,Yb) were measured using the solid state cell in the temperature range of 970 to 1323 K For formation of Cu2L?O5 compounds from their binary component oxides according to the reaction 2 CUO (s) + L%03 (s) -, Cu,,L%05 (s),the Gibbs' free energy changes can be represented by the following equations:AGO = 13 080 - 13.70 'I" (+80) J mol-' (Ln = Tb)AGq = 11 480 - 13.51 T (260) J mol-I (Ln = Dy)AGO = 10 750 - 13.99 T (260) J mol-I (Ln = Er)AGO = 9 920 - 13.90 T (260) J mol-' (Ln = Yb) Since formation of the compounds is endothermic, the compounds become thermodynamically unstable with respect to their component oxides below 955 K for Cu2Tb205, 850 K for Cu2Dy205, 768 K for Cu2Er205 and 714 K for Cu2Yb2OS When the oxygen partial pressure over Cu2L%05 is lowered, they decompose according to the scheme, 2 CU,L%O, (s) -r 2 L%03 (s) +2 cu20 (s) + 02(g)The equilibrium chemical potentials of oxygen corresponding to the dissociation reactions are computed from the emf data and auxiliary information on Cu20 and CuO. The computed decomposition temperatures at an oxygen partial pressure of 5.0 x ld Pa are compared with those obtained directly from combined thermogravimetric (TGA) and differential thermal analyses (DTA).The free energy, enthalpy and entropy of formation of Cu2Ln205 compounds show systematic variation with the ionic radius of the trivalent lanthanide ion. The trends obtained in this study are compared with information available in the literature. The staZbility of Cu2Ln205 compounds increases with the decrease in ionic radii of the ~ n ion~. +

Alternating current conduction behavior of excimer laser ablated SrBi2Nb2O9 thin films

Bi-layered Aurivillius compounds prove to be efficient candidates of nonvolatile memories. SrBi2Nb2O9 thin films were deposited by excimer laser ablation at low substrate temperature (400 °C) followed by an ex situ annealing at 750 °C. The polarization hysteresis behavior was confirmed by variation of polarization with the external applied electric field and also verified with capacitance versus voltage characteristics. The measured values of spontaneous and remnant polarizations were, respectively, 9 and 6 μC/cm2 with a coercive field of 90 kV/cm. The measured dielectric constant and dissipation factors at 100 kHz were 220 and 0.02, respectively. The frequency analysis of dielectric and ac conduction properties showed a distribution of relaxation times due to the presence of multiple grain boundaries in the films. The values of activation energies from the dissipation factor and grain interior resistance were found to be 0.9 and 1.3 eV, respectively. The deviation in these values was attributed to the energetic conditions of the grain boundaries and bulk grains. The macroscopic relaxation phenomenon is controlled by the higher resistive component in a film, such as grain boundaries at lower temperatures, which was highlighted in the present article in close relation to interior grain relaxation and conduction properties.

Growth and characterization of excimer laser-ablated BaBi2Nb2O9 thin films

The pulsed-laser ablation technique has been employed to deposit polycrystalline thin films of layered-structure ferroelectric BaBi2Nb2O9 (BBN). Low-substrate-temperature growth (Ts = 400 °C) followed by ex situ annealing at 800 °C for 30 min was performed to obtain a preferred orientation. Ferroelectricity in the films was verified by examining the polarization with the applied electric field and was also confirmed from the capacitance–voltage characteristics. The films exhibited well-defined hysteresis loops, and the values of saturation (Ps) and remanent (Pr) polarization were 4.0 and 1.2 μC/cm2, respectively. The room-temperature dielectric constant and dissipation factor were 214 and 0.04, respectively, at a frequency of 100 kHz. A phase transition from a ferroelectric to paraelectric state of the BBN thin film was observed at 220 °C. The dissipation factor of the film was observed to increase after the phase transition due to a probable influence of dc conduction at high temperatures. The real and imaginary part of the dielectric constant also exhibited strong frequency dispersion at high temperatures.

Temperature dependence of the energy gap and free carrier absorption in bulk InAs0.05Sb0.95 single crystals

Temperature dependence of the energy gap and free carrier absorption in a high-quality InAs0.05Sb0.95 single crystal was studied between 90 K and 430 K through the absorption spectra. At this alloy concentration, the room-temperature energy gap was measured to be 0.15 eV. Varshni- and the Bose–Einstein-type fit parameters were obtained from the measured temperature dependence of the energy gap, and the latter gave the zero-temperature gap to be 0.214 eV. It was found that although Weider’s empirical formula for the dependence of the energy gap on temperature and the alloy concentration agrees with the value of the gap at room temperature, it is inaccurate in describing its temperature dependence. From the free carrier absorption measurements, the phonon limited cross section of 7.35×10−16 cm2 at 15 μm was deduced at room temperature.

Backward switching phenomenon from field forced ferroelectric to antiferroelectric phases in antiferroelectric PbZrO3 thin films

Antiferroelectric materials (example: lead zirconate and modified lead zirconate stannate), in which a field-induced ferroelectric phase transition is feasible due to a small free energy difference between the ferroelectric and the antiferroelectric phases, are proven to be very good candidates for applications involving actuation and high charge storage devices. The property of reverse switching from the field-induced ferroelectric to antiferroelectric phases is studied as a function of temperature, applied electric field, and sample thickness in antiferroelectric lead zirconate thin films deposited by pulsed excimer laser ablation. The maximum released charge density was 22 μC/cm2 from a stored charge density of 36 μC/cm2 in a 0.55 μ thick lead zirconate thin film. This indicated that more than 60% of the stored charge could be released in less than 7 ns at room temperature for a field of 200 kV/cm. The content of net released charge was found to increase with increasing field strength, whereas with increasing temperature the released charge was found to decrease. Thickness-dependent studies on lead zirconate thin films showed that size effects relating to extrinsic and intrinsic pinning mechanisms controlled the released and induced charges through the intrinsic switching time. These results proved that antiferroelectric PZ thin films could be utilized in high-speed charge decoupling capacitors in microelectronics applications.

Growth and characterization of SrBi2Nb2O9 thin films by pulsed-laser ablation

Polycrystalline films of SrBi2Nb2O9 were grown using pulsed-laser ablation. The ferroelectric properties were achieved by low-temperature deposition followed by a subsequent annealing process. The lower switching voltage was obtained by lowering the thickness, which did not affect the insulating nature of the films. The hysteresis results showed an excellent square-shaped loop with results (Pr = 6 μC/cm2, Ec = 100 kV/cm) in good agreement with earlier reports. The films also exhibited a dielectric constant of 250 and a dissipation factor of 0.02. The transport studies indicated an ohmic behavior, while higher voltages induced a bulk space charge.

Field-induced dielectric properties of laser ablated antiferroelectric (Pb0.99Nb0.02)(Zr0.57Sn0.38Ti0.05)0.98O3 thin films

Niobium-modified lead zirconate stannate titanate antiferroelectric thin films with the chemical composition of (Pb0.99Nb0.02)(Zr0.57Sn0.38Ti0.05)0.98O3 were deposited by pulsed excimer laser ablation technique on Pt-coated Si substrates. Field-induced phase transition from antiferroelectric to ferroelectric properties was studied at different fields as a function of temperature. The field forced ferroelectric phase transition was elucidated by the presence of double-polarization hysteresis and double-butterfly characteristics from polarization versus applied electric field and capacitance and voltage measurements, respectively. The measured forward and reverse switching fields were 25 kV/cm and 77 kV/cm, respectively. The measured dielectric constant and dissipation factor were 540 and 0.001 at 100 kHz, respectively, at room temperature.