Topological close packed mu phase formation and the determination of diffusion parameters in the Co-Mo system

The study on the formation and growth of topological close packed (TCP) compounds is important to understand the performance of turbine blades in jet engine applications. These deleterious phases grow mainly by diffusion process in the superalloy substrate. Significant volume change was found because of growth of the p phase in Co-Mo system. Growth kinetics of this phase and different diffusion parameters, like interdiffusion, intrinsic and tracer diffusion coefficients are calculated. Further the activation energy, which provides an idea about the mechanism, is determined. Moreover, the interdiffusion coefficient in Co(Mo) solid solution and impurity diffusion coefficient of Mo in Co are determined.

Helix-coil stability constants for amino acids in nonaqueous solvents. Studies of random poly(-benzyl-L-glutamate-co-L-alanine) and poly(-benzyl-L-glutamate-co-L-leucine) in a mixed solvent

The host-guest technique has been applied to the determination of the helix-coil stability constants of two naturally occurring amino acids, L-alanine and L-leucine, in a nonaqueous solvent system. Random copolymers containing L-alanine and L-leucine, respectively, as guest residues and -benzyl-L-glutamate as the host residue were synthesized. The polymers were fractionated and characterized for their amino acid content, molecular weight, and helix-coil transition behavior in a dichloroacetic acid (DCA)-1,2-dichloroethane (DCE) mixture. Two types of helix-coil transitions were carried out on the copolymers: solvent-induced transitions in DCA-DCE mixtures at 25°C and thermally induced transitions in a 82:18 (wt %) DCA-DCE mixture. The thermally induced transitions were analyzed by statistical mechanical methods to determine the Zimm-Bragg parameters, and s, of the guest residues. The experimental data indicate that, in the nonaqueous solvent, the L-alanine residue stabilizes the -helical conformation more than the L-leucine residue does. This is in contrast to their behavior in aqueous solution, where the reverse is true. The implications of this finding for the analysis of helical structures in globular proteins are discussed.

Use of metastable equilibria for determination of Gibbs energy of solids

Attempts are made to measure activities of both components of a binary alloy (A�B) at 650 K using a solid-state galvanic cell incorporating a new composite solid electrolyte. Since the ionic conductivity of the composite solid electrolyte is three orders of magnitude higher than that of pure CaF2, the cell can be operated at lower temperatures. The alloy phase is equilibrated in separate experiments with flourides of each component and fluorine potential is measured. The mixture of the alloy (A�B) and the fluoride of the more reactive component (BF2) is stable, while (A�B) + AF2 mixture is metastable, Factors governing the possible use of metastable equilibria have been elucidated in this study. In the Co�Ni system, where the difference in Gibbs energies of formation of the fluorides is 21.4 kJ/mol, emf of the cell with metastable phases at the electrode is constant for periods ranging from 90 to 160 ks depending on alloy composition. Subsequently, the emf decreases because of the onset of the displacement reaction. In the Ni�Mn system, measurement of the activity of Ni using metastable equilibria is not fully successful at 650 K because of the large driving force for the displacement reaction (208.8 kJ/mol). Critical factors in the application of metastable equilibria are the driving force for displacement reaction and diffusion coefficients in both the alloy and fluoride solid solution.

High-resolution methyl edited GFT NMR experiments for protein resonance assignments and structure determination

Three-dimensional (3D) structure determination of proteins is benefitted by long-range distance constraints comprising the methyl groups, which constitute the hydrophobic core of proteins. However, in methyl groups (of Ala, Ile, Leu, Met, Thr and Val) there is a significant overlap of C-13 and H-1 chemical shifts. Such overlap can be resolved using the recently proposed (3,2)D HCCH-COSY, a G-matrix Fourier transform (GFT) NMR based experiment, which facilitates editing of methyl groups into distinct spectral regions by combining their C-13 chemical shifts with that of the neighboring, directly attached, C-13 nucleus. Using this principle, we present three GFT experiments: (a) (4,3)D NOESY-HCCH, (b) (4,3)D H-1-TOCSY-HCCH and (c) (4,3)D C-13-TOCSY-HCCH. These experiments provide unique 4D spectral information rapidly with high sensitivity and resolution for side-chain resonance assignments and NOE analysis of methyl groups. This is exemplified by (4,3)D NOESY-HCCH data acquired for 17.9 kDa non-deuterated cytosolic human J-protein co-chaperone, which provided crucial long-range distance constraints for its 3D structure determination.

Potentiometric determination of activities in the two-phase fields of the system Na2O---(α)Al2O3

Three compounds have been found to be stable in the pseudobinary system Na2O---(α)Al2O3 between 825 and 1400 K; two nonstoichiometric phases, β-alumina and β″-alumina, and NaAlO2. The homogeneity of β-alumina ranges from 9.5 to 11 mol% Na2O, while that of β″-alumina from 13.3 to 15.9 mol% Na2O at 1173 K. The activity of Na2O in the two-phase fields has been determined by a solid-state potentiometric technique. Since both β- and β″-alumina are fast sodium ion conductors, biphasic solid electrolyte tubes were used in these electrochemical measurements. The open circuit emf of the following cells were measured from 790 to 980 K: [GRAPHICS] The partial molar Gibbs' energy of Na2O relative to gamma-Na2O in the two-phase regions can be represented as: DELTA-GBAR(Na2O)(alpha- + beta-alumina) = -270,900 + 24.03 T, DELTA-GBAR(Na2O)(beta- + beta"-alumina) = -232,700 + 56.19 T, and DELTA-GBAR(Na2O)(beta"-alumina + NaAlO2) = -13,100 - 4.51 T J mol-1. Similar galvanic cells using a Au-Na alloy and a mixture of Co + CoAl(2+2x)O4+3x + (alpha)Al2O3 as electrodes were used at 1400 K. Thermodynamic data obtained in these studies are used to evaluate phase relations and partial pressure of sodium in the Na2O-(alpha) Al2O3 system as a function of oxygen partial pressure, composition and temperature.

Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly (butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

Chemical toughening of epoxies. I. Structural modification of epoxy resins by reaction with hydroxy-terminated poly(butadiene-co-acrylonitrile)

In an attempt to toughen the epoxy resin matrix for fiber-reinforced composite applications, a chemical modification procedure of a commercially available bisphenol-A-based epoxy resin using reactive liquid rubber HTBN [hydroxy-terminated poly(butadiene-co-acrylonitrile)] and TDI (tolylene diisocyanate) is described. The progress of the reaction and the structural changes during modification process are studied using IR spectroscopy, viscosity data, and chemical analysis (epoxy value determination). The studies support the proposition that TDI acts as a coupling agent between the epoxy and HTBN, forming a urethane linkage with the former and an oxazolidone ring with the latter. The chemical reactions that possibly take place during the modification are discussed.

The Determination of the Surface Tensions of Nickel Sulfur Alloys using the Electromagnetic Oscillating Droplet Technique

An oscillating droplet method combined with electromagnetic levitation technique has been applied to determine the surface tensions of liquid nickel sulphur alloys as a function of the temperature and composition. The natural frequency of the oscillating droplet is evaluated using a Fourier analyser, and the influence of magnetic field strength on the surface tension was considered. Furthermore, the applicability of Butler's equation and subregular solution model for the surface was shown to predict the surface tension of the systems containing the surface active elements.

Determination of the reactivity ratios for the oxidative copolymerizations of indene with methyl, ethyl and butyl acrylates

Full Paper: The copolyperoxides of various compositions of indene with methyl acrylate, ethyl acrylate and butyl acrylate have been synthesized by the free-radical-initiated oxidative copolymerization. The compositions of copolyperoxide obtained from H-1 and C-13 NMR spectra have been used to determine the reactivity ratios of the monomers. The copolyperoxides contain a greater proportion of the indene units in random placement. The NMR studies have shown irregularities in the copolyperoxide chain due to the cleavage reactions of the propagating peroxide radical. The thermal analysis by differential scanning calorimetry suggests alternating peroxide units in the copolyperoxide chain. From the activation energy for the thermal degradation, it was inferred that degradation occurs via the dissociation of the peroxide (O-O) bonds of the copolyperoxide chain. The flexibility of the polyperoxides in terms of glass transition temperature (T-g) has also been examined.

A tropical oviparous lizard, Calotes versicolor, exhibiting a potentially novel FMFM pattern of temperature-dependent sex determination

Among squamate reptiles, lizards exhibit an impressive array of sex-determining modes viz. genotypic sex determination, temperature-dependent sex determination, co-occurrence of both these and those that reproduce parthenogenetically. The oviparous lizard, Calotes versicolor, lacks heteromorphic sex chromosomes and there are no reports on homomorphic chromosomes. Earlier studies on this species presented little evidence to the sex-determining mechanism. Here we provide evidences for the potential role played by incubation temperature that has a significant effect (P<0.01) on gonadal sex and sex ratio. The eggs were incubated at 14 different incubation temperatures. Interestingly, 100% males were produced at low (25.5 +/- 0.5 degrees C) as well as high (34 +/- 0.5 degrees C) incubation temperatures and 100% females were produced at low (23.5 +/- 0.5 degrees C) and high (31.5 +/- 0.5 degrees C) temperatures, clearly indicating the occurrence of TSD in this species. Sex ratios of individual clutches did not vary at any of the critical male-producing or female-producing temperatures within as well as across the seasons. However, clutch sex ratios were female- or male-biased at intermediate temperatures. Thermosensitive period occurred during the embryonic stages 3033. Three pivotal temperatures operate producing 1:1 sex ratio. Histology of gonad and accessory reproductive structures provide additional evidence for TSD. The sex-determining pattern, observed for the first time in this species, that neither compares to Pattern I [Ia (MF) and Ib (FM)] nor to Pattern II (FMF), is being referred to as FMFM pattern of TSD. This novel FMFM pattern of sex ratio exhibited by C. versicolor may have an adaptive significance in maintaining sex ratio. J. Exp. Zool. 317:3246, 2012. (c) 2011 Wiley Periodicals, Inc.

DETERMINATION OF THE STRONG COUPLING FROM HADRONIC TAU DECAYS USING RENORMALIZATION GROUP SUMMED PERTURBATION THEORY

Be the strong coupling constant alpha(s) from the tau hadronn width using a renormalization group summed (RGS) expansion of the QCD Adler lunction. The main theoretical uncertainty in the extraction of as is due to the manner in which renormalization group invariance is implemented, and the as yet uncalculated higher order terms in the QCD perturbative series. We show that new expansion exhibits good renormalization group improvement and the behavior of the series is similar to that of the standard RGS expansion. The value of the strong coupling in (MS) over bar scheme obtained with the RCS expansion is alpha(s) (M-tau(2)) = 0.338 +/- 0.010. The convergence properties of the new expansion can be improved by Bond transformation and analytic continuation in t he Bond plane. This is discussed elsewhere in these issues.

Wave propagation of phonon and phason displacement modes in quasicrystals: Determination of wave parameters

The paper presents the study of wave propagation in quasicrystals. Our interest is in the computation of the wavenumber (k(n)) and group speed (c(g)) of the phonon and phason displacement modes of one, two, and three dimensional quasicrystals. These wave parameter expressions are derived and computed using the elasto-hydrodynamic equations for quasicrystals. For the computation of the wavenumber and group speeds, we use Fourier transform approximation of the phonon and the phason displacement modes. The characteristic equations obtained are a polynomial equation of the wavenumber (k(n)), with frequency as a parameter. The corresponding group speeds (c(g)) for different frequencies are then computed from the wavenumber k(n). The variation of wavenumber and group speeds with frequency is plotted for the 1-D quasicrystal, 2-D decagonal Al-Ni-Co quasicrystals, and 3-D icosahedral Al-Pd-Mn and Zn-Mg-Sc quasicrystals. From the wavenumber and group speeds plots, we obtain the cut-off frequencies for different spatial wavenumber eta(m). The results show that for 1-D, 2-D, and 3-D quasicrystals, the phonon displacement modes are non-dispersive for low values of eta(m) and becomes dispersive for increasing values of eta(m). The cut-off frequencies are not observed for very low values of eta(m), whereas the cut-off frequency starts to appear with increasing eta(m). The group speeds of the phason displacement modes are orders of magnitude lower than that of the phonon displacement modes, showing that the phason modes do not propagate, and they are essentially the diffusive modes. The group speeds of the phason modes are also not influenced by eta(m). The group speeds for the 2-D quasicrystal at 35 kHz is also simulated numerically using Galerkin spectral finite element methods in frequency domain and is compared with the results obtained using wave propagation analysis. The effect of the phonon and phason elastic constants on the group speeds is studied using 3-D icosahedral Al-Pd-Mn and Zn-Mg-Sc quasicrystals. It is also shown that the phason elastic constants and the coupling coefficient do not affect the group speeds of the phonon displacement modes. (C) 2015 AIP Publishing LLC.

Solute induced liquid crystalline behaviour of a quaternary ammonium salt and its application to structure determination

A new liquid crystalline phase, induced by the addition of small amounts of a non-mesogenic solute (such as dimethyl sulphoxide or methyl iodide) to a quaternary ammonium salt, N-methyl-N,N,N-trioctadecylammonium iodide (MTAI), has been detected by NMR and optical microscopic studies. In some cases, there is a coexistence of nematic and smectic phases. Information on the ordering of the phases in the magnetic field of the spectrometer has been derived from NMR spectra of a dissolved molecule, C-13-enriched methyl iodide. The low order parameter of the pure thermotropic nematic phase of the salt provides first-order spectra of the dissolved oriented molecules. Analyses of spectra of cis,cis-mucononitrile exemplifies the utility of the MTAI nematic phase in the determination of structural parameters of the solute.

Determination of diffusion parameters and activation energy of diffusion in V3Si phase with A15 crystal structure

Diffusion such is the integrated diffusion coefficient of the phase, the tracer diffusion coefficient of species at different temperatures and the activation energy for diffusion, are determined in V3Si phase with A15 crystal structure. The tracer diffusion coefficient of Si Was found to be negligible compared to the tracer diffusion coefficient of V. The calculated diffusion parameters will help to validate the theoretical analysis of defect structure of the phase, which plays an important role in the superconductivity.

Einstein Relation in n-Channel Inversion Layers of Nonlinear Optical, Optoelectronic and Related Materials: Simplified Theory, Relative Comparison and Suggestion for an Experimental Determination

In this paper, we study the Einstein relation for the diffusivity to mobility ratio (DMR) in n-channel inversion layers of non-linear optical materials on the basis of a newly formulated electron dispersion relation by considering their special properties within the frame work of k.p formalism. The results for the n-channel inversion layers of III-V, ternary and quaternary materials form a special case of our generalized analysis. The DMR for n-channel inversion layers of II-VI, IV-VI and stressed materials has been investigated by formulating the respective 2D electron dispersion laws. It has been found, taking n-channel inversion layers of CdGeAs2, Cd(3)AS(2), InAs, InSb, Hg1-xCdxTe, In1-xGaxAsyP1-y lattice matched to InP, CdS, PbTe, PbSnTe, Pb1-xSnxSe and stressed InSb as examples, that the DMR increases with the increasing surface electric field with different numerical values and the nature of the variations are totally band structure dependent. The well-known expression of the DMR for wide gap materials has been obtained as a special case under certain limiting conditions and this compatibility is an indirect test for our generalized formalism. Besides, an experimental method of determining the 2D DMR for n-channel inversion layers having arbitrary dispersion laws has been suggested.