Reactive Diffusion Between Vanadium and Silicon

Interdiffusion study is conducted in the V-Si system to determine integrated diffusion coefficients of the phases. Activation energy values are calculated from the experiments conducted at different temperatures. The average values are found to be 208, 240 and 141 kJ/mol, respectively, for the V(3)Si, V(5)Si(3) and VSi(2) phases. The low activation energy for the VSi(2) phase indicates very high concentration of defects or the significant contribution from the grain boundary diffusion. The error in calculation of diffusion parameters from a very thin phase layer in a multiphase diffusion couple is discussed. Further the data available in the literature in this system is compared and the problems in the indirect methodology followed previously to calculate the diffusion parameters are discussed.

Evidence of residual entropy in the cubic spinel Zn2TiO4

The standard free energies of formation of Zn2Ti04 and ZnTi03 have been determined in the temperature range 930° to i ioo'x from electromotive force measurements on reversible solid oxide galvanic cells;Ag-5at%znll I Pt, + CaO-Zr02 ZnO I II Ag-5at%Zn Y20r Th02 CaO-Zr02 + ,Pt Zn2Ti04+ ZnTi03 and II Ag-5at%Zn CaO-Zr02 + ,Pt ZnTi03+ Ti02 The values may be expressed by the equations,2ZnO (wurtz) + Ti02(rut) -> Zn2Ti04(sp), f:!:.Go = -750-2-46T (±75)cal;ZnO(wurtz) +Ti02(rut) -> ZnTi03(ilmen) ,f:!:.Co = -]600-0·]99T(±50)cal.Combination of the free energy values with the calorimetric heat of formation, and low-temperature and high-temperature heat capacity of Zn2Ti04 reported in literature, suggests a residual entropy of ],9 (±0·6) cal K-1 mol ? for the cubic spinel. Ideal mixing of Zn2+ and Ti4+ ions on the octahedral sites would result in a configurational contribution to the entropy of 2· 75 cal K-1 rnol ".The difference is indicative of short-range ordering of cations on octahedral sites.

Crystal Structure, Thermal Expansion and ElectricaH Conductivity of Yo.sCao.2Fel-x Mnx03+o (0 < x < 1.0)

The crystal structure, thennal expansion and electrical conductivity of the solid solutions YOgCao.2Fel-x MnxOJ+c5 (0 ~ x ~ 1.0) were investigated. All compositions had the GdFeOrtype orthorhombic perovskite structure with trace amounts of a second phase present in case of x = 0.8 and 1.0. The lattice parameters were detennined at room tempe'rature by using X-ray powder diffraction (XRPD). The pseudocubic lattice constant decreased with increasing x. The average I inear thermal expansion coefficient (anv) in the temperature range from 673 to 973 K showed negligible change with x up to x = 0.4. The thennal expansion curve for x = I had a slope approaching zero in the temperature range from 648 to 948 K. The calculated activation energy values for electrical conduction indicate that conduction occurs primarily by the small polaron hopping mechanism. The drastic drop in electrical conductivity for a small addition of Mn (0 ~ x ~ 0.2) is caused by the preferential fonnation of Mn4t ion~ (rather than Fe4 +) which act as carrier traps. This continues till the charge compensation for the divalent ions on the A-site is complete. The results indicate that with further increase in manganese content (beyond x =0.4) in the solid solutions, there is an increase in exc :::ss oxygen and consequently, a small increase in Mn'll il>I1~, which are charge compensated by the formation of cation vancancies.

Leakage current behavior in pulsed laser deposited Ba(Zr0.05Ti0.95)O3 thin films

Barium zirconium titanate [Ba(Zr0.05Ti0.95)O3, BZT] thin films were prepared by pulsed laser ablation technique and dc leakage current conduction behavior was extensively studied. The dc leakage behavior study is essential, as it leads to degradation of the data storage devices. The current-voltage (I-V) of the thin films showed an Ohmic behavior for the electric field strength lower than 7.5 MV/m. Nonlinearity in the current density-voltage (J-V) behavior has been observed at an electric field above 7.5 MV/m. Different conduction mechanisms have been thought to be responsible for the overall I-V characteristics of BZT thin films. The J-V behavior of BZT thin films was found to follow Lampert’s theory of space charge limited conduction similar to what is observed in an insulator with charge trapping moiety. The Ohmic and trap filled limited regions have been explicitly observed in the J-V curves, where the saturation prevailed after a voltage of 6.5 V referring the onset of a trap-free square region. Two different activation energy values of 1.155 and 0.325 eV corresponding to two different regions have been observed in the Arrhenius plot, which was attributed to two different types of trap levels present in the film, namely, deep and shallow traps.

A resistometric study of solute–solute interaction in dilute aluminium–silver alloys

The experimentally determined apparent vacancy formation energy values in dilute aluminium—silver alloys showed a divergence from calculated values at higher solute fractions. This is explained in terms of a solute—solute interaction energy of the order of 0.10 ev which exists when the binding energy between a vacancy and a solute atom pair is reduced to zero.

Temperature and potential dependence electrochemical impedance studies of LiMn2O4

Detailed analysis of alternating current impedance data of LiMn2O4 electrodes measured at several temperatures and potentials was carried out. The Nyquist plots generally consisted of semicircles corresponding to two time constants. However, at low temperatures (-10 to 10 A degrees C) and potential region between 3.90 and 4.20 V, three time constants were present. The third semicircle present at the middle to high frequency range was attributed to electronic resistance of LiMn2O4. Impedance parameters were evaluated using appropriate electrical equivalent circuits. From the temperature dependence of resistive parameters, activation energy values for the corresponding processes were calculated.

Dynamic recovery and recrystallization during high-temperature tensile deformation of a free-standing Pt-aluminide bond coat

Free-standing Pt-aluminide (PtAl) bond coat, when subjected to tensile testing at high temperatures (T >= 900 degrees C), exhibits significant decrease in strength and increase in ductility during deformation at strains exceeding that corresponding to the ultimate tensile strength (UTS), i.e., in the post-UTS regime. The stress-strain curve is also marked by serrations in this regime. Electron back scattered diffraction (EBSD) and transmission electron microscopy (TEM) studies suggest dynamic recovery and recrystallization (DRR) as the mechanisms for the observed tensile behavior in the coating. Activation energy values suggest vacancy diffusion assists DRR. The fine recrystallized grains formed after deformation had a strong < 110 > texture. (c) 2014 Elsevier B.V. All rights reserved.

Tautomeric Preference and Conformation Locking in Fenobam, Thiofenobam, and Their Analogues: The Decisive Role of Hydrogen Bond Hierarchy

The crystal and molecular structures of the potential antidepressant drug fenobam and its derivatives are examined in terms of the preferred form among the two possible tautomeric structures. In this study, chemical derivatization has been utilized as a means to ``experimentally simulate'' the tautomeric preference and conformational variability in fenobam. Eight new derivatives of fenobam have been synthesized, and structural features have been characterized by single-crystal X-ray diffraction and NMR spectroscopy. The specific tautomeric preference found in all of these compounds and their known crystal forms have been construed in terms of the stabilizing intramolecular N-H center dot center dot center dot O and N-H center dot center dot center dot S hydrogen bonding. The hierarchy of intramolecular hydrogen bonds evidenced as the preference of the C-H center dot center dot center dot O hydrogen bond over C-H center dot center dot center dot N and that of the C-H center dot center dot center dot N hydrogen bond over C-H center dot center dot center dot S explains the two distinct conformations adopted by fenobam and thiofenobam derivatives. The relative energy values of different molecular conformations have been calculated and compared.

Free Energy Gap Dependence of the Electron-Transfer Rate from the Inverted to the Normal Region

numerical study of the free energy gap (FEG) dependence of the electron-transfer rate in polar solvents is presented. This study is based on the generalized multidimensional hybrid model, which not only includes the solvent polarization and the molecular vibration modes, but also the biphasic polar response of the solvent. The free energy gap dependence is found to be sensitive to several factors, including the solvent relaxation rate, the electronic coupling between the surfaces, the frequency of the high-frequency quantum vibrational mode, and the magnitude of the solvent reorganization energy. It is shown that in some cases solvent relaxation can play an important role even in the Marcus normal regime. The minimal hybrid model involves a large number of parameters, giving rise to a diverse non-Marcus FEG behavior which is often determined collectively by these parameters. The model gives the linear free energy gap dependence of the logarithmic rate over a substantial range of FEG, spanning from the normal to the inverted regime. However, even for favorable values of the relevant parameters, a linear free energy gap dependence of the rate could be obtained only over a range of 5000-6000 cm(-1) (compared to the experimentally observed range of 10000 cm(-1) reported by Benniston et al.). The present work suggests several extensions/generalizations of the hybrid model which might be necessary to fully understand the observed free energy gap dependence.

Constraining the low-energy pion electromagnetic form factor with space-like and phase of time-like data

The Taylor coefficients c and d of the EM form factor of the pion are constrained using analyticity, knowledge of the phase of the form factor in the time-like region, 4m(pi)(2) <= t <= t(in) and its value at one space-like point, using as input the (g - 2) of the muon. This is achieved using the technique of Lagrange multipliers, which gives a transparent expression for the corresponding bounds. We present a detailed study of the sensitivity of the bounds to the choice of time-like phase and errors present in the space-like data, taken from recent experiments. We find that our results constrain c stringently. We compare our results with those in the literature and find agreement with the chiral perturbation-theory results for c. We obtain d similar to O(10) GeV-6 when c is set to the chiral perturbation-theory values.

Electron Mean Energy, Secondary Ionization Coefficients And (E/P)Crit In Binary-Mixtures Of Sf6-N2 And Ccl2f2-N2

Measurements of the ratio of diffusion coefficient to mobility (D/ mu ) of electrons in SF6-N2 and CCl2F2-N2 mixtures over the range 80Values of (E/p)c.mix (the critical E/p of the mixture, where alpha = eta ), and the electron mean energies epsilon c.mix corresponding to (E/p)c.mix, are found to vary with the percentage of the electronegative gas in the mixture (F) according to the following relationship: (E/p)c.mix=(E/p)c.N(2)+((E/p)c.A-(E/p)c.N(2)) (1-exp(- beta F/100-F)) and epsilon c.mix= epsilon c.N(2)+( epsilon c.A- epsilon c.N(2)) (1-exp(- beta F/100-F)) where A refers to the attaching gas, either SF6 or CCl2F2 and beta is a constant, equal to 2.43 for SF6 mixtures and 5.12 for CCl2F2 mixtures. In the present study, it has been possible to show that beta is indeed to a factor of synergism. Estimated gamma values (secondary ionisation coefficients) did not show any significant variation with F for F<50.

Improved bounds on the radius and curvature of the K pi scalar form factor and implications to low-energy theorems

We obtain stringent bounds in the < r(2)>(K pi)(S)-c plane where these are the scalar radius and the curvature parameters of the scalar K pi form factor, respectively, using analyticity and dispersion relation constraints, the knowledge of the form factor from the well-known Callan-Treiman point m(K)(2)-m(pi)(2), as well as at m(pi)(2)-m(K)(2), which we call the second Callan-Treiman point. The central values of these parameters from a recent determination are accomodated in the allowed region provided the higher loop corrections to the value of th form factor at the second Callan-Treiman point reduce the one-loop result by about 3% with F-K/F-pi = 1.21. Such a variation in magnitude at the second Callan-Treiman point yields 0.12 fm(2) less than or similar to < r(2)>(K pi)(S) less than or similar to 0.21 fm(2) and 0.56 GeV-4 less than or similar to c less than or similar to 1.47 GeV-4 and a strong correlation between them. A smaller value of F-K/F-pi shifts both bounds to lower values.

Precise Values of the "C Component Vicinal Coupling Constants for Calculating Side-Chain Conformations in Amino Acids

From consideration of 'H-lH vicinal coupling constants and '"G'H long-range coupling constants in a series of amino acid derivatives, the precise values of uC component vicinal coupling constants have been calculated for the three minimum energy staggered rotamers for the C(or)H-C(P)H, side-chains of amino acids.

Metallo crown porphyrins as ionophores-metal dependent uncoupling of mitochondrial energy potential

Porphyrins appended with crown ether moieties function as efficient uncouplesrs of oxidative phorphorylation in rat liver mitochondria. Permeation of these highly organized porphyrins decrease the respiratory coefficient index (RCI) values. Lowering of the RCI values parallels the number of K+ chelating crown ether groups attached to the porphyrins. The inhibitory effect upon the oxidative phorphorylation reaction depends on the nature of divalent metal ions, VO, Co, Cu and Zn in the porphyrin cavity and related to their relative tendency to complex intracellular K+ ions.

Metallo crown porphyrins as ionophores-metal dependent uncoupling of mitochondrial energy potential

Porphyrins appended with crown ether moieties function as efficient uncouplesrs of oxidative phorphorylation in rat liver mitochondria. Permeation of these highly organized porphyrins decrease the respiratory coefficient index (RCI) values. Lowering of the RCI values parallels the number of K+ chelating crown ether groups attached to the porphyrins. The inhibitory effect upon the oxidative phorphorylation reaction depends on the nature of divalent metal ions, VO, Co, Cu and Zn in the porphyrin cavity and related to their relative tendency to complex intracellular K+ ions.