Estimation of the 2.0(5) helix type i -> i hydrogen bond energy at Aib*-Oxa motif: an isodesmic approach

Bending at the valence angle N-C-alpha-C' (tau) is a known control feature for attenuating the stability of the rare intramolecular hydrogen bonded pseudo five-membered ring C-5 structures, the so called 2.0(5) helices, at Aib. The competitive 3(10)-helical structures still predominate over the C5 structures at Aib for most values of tau. However at Aib*, a mimic of Aib where the carbonyl 0 of Aib is replaced with an imidate N (in 5,6-dihydro-4H-1,3-oxazine = Oxa), in the peptidomimic Piv-Pro-Aib*-Oxa (1), the C(5)i structure is persistent in both crystals and in solution. Here we show that the i -> i hydrogen bond energy is a more determinant control for the relative stability of the C5 structure and estimate its value to be 18.5 +/- 0.7 kJ/mol at Aib* in 1, through the computational isodesmic reaction approach, using two independent sets of theoretical isodesmic reactions. (C) 2014 Elsevier Ltd. All rights reserved.

Co-existence of tetragonal and monoclinic phases and multiferroic properties for x <= 0.30 in the (1-x)Pb(Zr0.52Ti0.48)O-3-(x)BiFeO3 system

Compositions with x <= 0.30 in the system (1- x)Pb(Zro(0.52)Ti(0.48))O-3-(x)BiFeO3 were synthesized by sol-gel method. Rietveld analysis of X-ray diffraction data reveals tetragonal structure (P4mm) for x <= 0.05 and monoclinic (Cm) phase along with the existence of tetragonal phase for 0.10 <= x <= 0.25 and monoclinic phase for x = 0.30. Transformation of E(2TO) and E + B1 vibrational modes in the range 210-250 cm(-1) (present for x <= 0.25) into A' + A `' modes at similar to 236 cm(-1) for x = 0.30, and occurrence of new vibrational modes A' and A `' in Raman spectra for x >= 0.10 unambiguously support the presence of monoclinic phase. Occurrence of remnant polarisation and enhanced magnetization with concentration of BiFeO3 indicates superior multiferroic properties. Variation of magneto-capacitance with applied magnetic field is a strong evidence of magneto-electric multiferroic coupling in these materials. (C) 2014 Elsevier B.V. All rights reserved.

Microstructural Features of Hot Deformed Nb-1Zr-0.1C Alloy

Niobium-based alloys are well-established refractory materials; as a result of their high melting temperature and good creep properties, these alloys find their applications in nuclear reactors. The present study deals with a microstructural response of these materials during hot working. The evolution of microstructure and texture during high-temperature deformation has been investigated in the temperature range 1500-1700A degrees C and strain rate range of 0.001-0.1 s(-1). For each deformed sample, the microstructure has been examined in detail. The microstructural features clearly revealed the formation of a substructure and the occurrence of dynamic recrystallization in a proper temperature-strain rate window. At low strain rates, the necklace structure formation was more prominent.

Improved quasiparticle wave functions and mean field for G(0)W(0) calculations: Initialization with the COHSEX operator

The GW approximation to the electron self-energy has become a standard method for ab initio calculation of excited-state properties of condensed-matter systems. In many calculations, the G W self-energy operator, E, is taken to be diagonal in the density functional theory (DFT) Kohn-Sham basis within the G0 W0 scheme. However, there are known situations in which this diagonal Go Wo approximation starting from DFT is inadequate. We present two schemes to resolve such problems. The first, which we called sc-COHSEX-PG W, involves construction of an improved mean field using the static limit of GW, known as COHSEX (Coulomb hole and screened exchange), which is significantly simpler to treat than GW W. In this scheme, frequency-dependent self energy E(N), is constructed and taken to be diagonal in the COHSEX orbitals after the system is solved self-consistently within this formalism. The second method is called off diagonal-COHSEX G W (od-COHSEX-PG W). In this method, one does not self-consistently change the mean-field starting point but diagonalizes the COHSEX Hamiltonian within the Kohn-Sham basis to obtain quasiparticle wave functions and uses the resulting orbitals to construct the G W E in the diagonal form. We apply both methods to a molecular system, silane, and to two bulk systems, Si and Ge under pressure. For silane, both methods give good quasiparticle wave functions and energies. Both methods give good band gaps for bulk silicon and maintain good agreement with experiment. Further, the sc-COHSEX-PGW method solves the qualitatively incorrect DFT mean-field starting point (having a band overlap) in bulk Ge under pressure.

Effects of Microstructure and Loading on Fracture of Sn-3.8Ag-0.7Cu Joints on Cu Substrates with ENIG Surface Finish

When dropped, electronic packages often undergo failure by propagation of an interfacial crack in solder joints under a combination of tensile and shear loading. Hence, it is crucial to understand and predict the fracture behavior of solder joints under mixed-mode high-rate loading conditions. In this work, the effects of the loading conditions (strain rate and loading angle) and microstructure interfacial intermetallic compound (IMC) morphology and solder yield strength] on the mixed-mode fracture toughness of Sn-3.8 wt.%Ag-0.7 wt.%Cu solder joints sandwiched between two Cu substrates with electroless nickel immersion gold (ENIG) metallization have been studied, and compared with the fracture behavior of joints attached to bare Cu. Irrespective of the surface finish, the fracture toughness of the solder joints decreased monotonically with strain rate and mode-mixity, both resulting in increased fracture proportion through the interfacial IMC layer. Furthermore, the proportion of crack propagation through the interfacial IMC layer increased with increase in the thickness and the roughness of the interfacial IMC layer and the yield strength of the solder, resulting in a decrease in the fracture toughness of the joint. However, under most conditions, solder joints with ENIG finish showed higher resistance to fracture than joints attached directly to Cu substrates without ENIG metallization. Based on the experimental observations, a fracture mechanism map is constructed correlating the yield strength of the solder, the morphology and thickness of the interfacial IMC, and the fracture mechanisms as well as the fracture toughness values for different solder joints under mode I loading.

Frequency and Temperature-Independent Electrical Transport Properties of 2BaO-0.5Na(2)O-2.5Nb(2)O(5)-4.5B(2)O(3) Glass-Ceramics

The temperature (300-973K) and frequency (100Hz-10MHz) response of the dielectric and impedance characteristics of 2BaO-0.5Na(2)O-2.5Nb(2)O(5)-4.5B(2)O(3) glasses and glass nanocrystal composites were studied. The dielectric constant of the glass was found to be almost independent of frequency (100Hz-10MHz) and temperature (300-600K). The temperature coefficient of dielectric constant was 8 +/- 3ppm/K in the 300-600K temperature range. The relaxation and conduction phenomena were rationalized using modulus formalism and universal AC conductivity exponential power law, respectively. The observed relaxation behavior was found to be thermally activated. The complex impedance data were fitted using the least square method. Dispersion of Barium Sodium Niobate (BNN) phase at nanoscale in a glass matrix resulted in the formation of space charge around crystal-glass interface, leading to a high value of effective dielectric constant especially for the samples heat-treated at higher temperatures. The fabricated glass nanocrystal composites exhibited P versus E hysteresis loops at room temperature and the remnant polarization (P-r) increased with the increase in crystallite size.

Experimental and theoretical studies on static and dynamic pressure-concentration isotherms of MmNi(5-x)Al(x) (x=0, 0.3, 0.5 and 0.8) hydrides

The static and dynamic pressure concentration isotherms (PCIs) of MmNi(5-x)Al(x). (x = 0, 0.3, 0.5 and 0.8) hydrides were measured at different temperatures using volumetric method. The effect of Al substitution on PCI and thermodynamic properties were studied. The plateau pressure and maximum hydrogen storage capacity decreased with Al content whereas reaction enthalpy increased. The plateau pressure, plateau slope and hysteresis effect was observed more for dynamic PCIs compared to static PCIs. Different mathematical models used for metal hydride-based thermodynamic devices simulation are compared to select suitable model for static and dynamic PCI simulation of MmNi(5)-based hydrides. Few important physical coefficients (partial molar volume, reaction enthalpy, reaction entropy, etc.) useful for development of thermodynamic devices were estimated. A relation has been proposed to correlate aluminium content and physical coefficients for the prediction of unknown PCI. The simulated and experimental PCIs were found matching closely for both static and dynamic conditions. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Structural, magnetic and electrochemical investigation of novel binary Na2-x(Fe1-yMny)P2O7 (0 <= y <= 1) pyrophosphate compounds for rechargeable sodium-ion batteries

Pyrophosphate cathodes have been recently reported as a competent family of insertion compounds for sodium-ion batteries. In the current study, we have investigated the binary Na2 - x(Fe1 - yMny)P2O7 (0 <= y <= 1) pyrophosphate family, synthesized by the classical solid-state method. They form a continuous solid solution maintaining triclinic P-1 (#2) symmetry. The local structural coordination differs mainly by different degrees of Na site occupancy and preferential occupation of the Fe2 site by Mn. The structural and magnetic properties of these mixed-metal pyrophosphate phases have been studied. In each case, complete Fe3+/Fe2+ redox activity has been obtained centered at 3 V vs. Na. The Fe3+/Fe2+ redox process involves multiple steps between 2.5 and 3 V owing to Na-cation ordering during electrochemical cycling, which merge to form a broad single Fe3+/Fe2+ redox peak upon progressive Mn-doping. (C) 2014 Elsevier B.V. All rights reserved.

An alluaudite Na-2+Fe-2x(2-x)(SO4)(3)(x=0.2) derivative phase as insertion host for lithium battery

A new desodiated derivative compound, Na0.89Fe1.8(SO4)(3), was prepared by the chemical oxidation of alluaudite Na2.4Fe1.8(SO4)(3) Phase using NOBF4 as oxidant. The structure and valency of Fe were characterized by X-ray diffraction (XRD) and Fe-57 Mossbauer spectroscopy. Intercalation behavior of lithium ions in the structure of Na0.89Fe1.8(SO4)(3) was gauged by electrochemical analyses and ex-situ X-ray diffraction. A high capacity of 110 mAh g(-1) at 0.1 C was obtained with a good rate kinetics within a range of 0.1-10 C(1 C = 118 mAh g-1) involving a high Fe3+/Fe2+ redox potential of 3.75 V (vs. Li/Li+). These results confirmed that the Na2.4-delta Fe1.8(SO4)(3) framework was stable even after oxidation and forms a new competitive cathode for the reversible intercalation of lithium ions. (C) 2014 Elsevier B.V. All rights reserved.

Controlling phase separation in La5/8-yPryCa3/8MnO3 (y=0.45) epitaxial thin films by strain disorder

Present study reveals that the length-scale of phase separation in La5/8-yPryCa3/8MnO3 thin films can be controlled by strain disorder invoked during the growth and relaxation process of film. Strain disorder provides an additional degree of freedom to tune colossal magnetoresistance. Magneto-transport measurements following cooling and heating in unequal fields protocol demonstrate that coherent strain stabilizes antiferromagnetic insulating phase, while strain disorder favors ferromagnetic metallic phase. Compared to bulk, antiferromagnetic-insulating phase freezes at lower temperatures in strain disordered films. Raman spectroscopy confirms the coexistence of charge-ordered-insulating and ferromagnetic-metallic phases which are structurally dissimilar and possess P2(1)/m and R-3C like symmetries, respectively. (C) 2015 AIP Publishing LLC.

Investigation of dielectric relaxation, Jahn-Teller distortion, and magnetic ordering in Y substituted Pr1-xYxMnO3 (0.1 <= x <= 0.4)

We report structural, magnetic, and dielectric properties of the perovskite compound Pr1-xYxMnO3 (0.1 <= x <= 0.4) studied using dc magnetization, ac susceptibility, neutron powder diffraction, and dielectric techniques. These compounds crystallize in orthorhombic space group (Pnma) in the temperature range 5-300 K. The Mn-O-Mn bond angle decreases with the Y substitution along with an increase in the Jahn-Teller distortion. The Jahn-Teller distortion for Pr0.9Y0.1MnO3 shows an anomalous change near 50 K, below which it falls sharply. Neutron powder diffraction patterns of all reported compositions at low temperature constitute additional magnetic Bragg peaks that suggest magnetic ordering. Magnetic reflections were indexed in the nuclear lattice with the propagation vector k = (0, 0, 0). Rietveld refinement of powder patterns conform to A type antiferromagnetic ordering where moments are aligned ferromagnetically in a-c plane and coupled nearly antiferromagnetically along b-axis resulting in a net ferromagnetic component along the b-direction. The antiferromagnetic transition temperature was deduced from dc magnetization and ac susceptibility data. The transition temperature decreases by nearly 22 K (from 81 K to 59 K) as yttrium content (x) increases from 0.1 to 0.4. Measurements reveal strong frequency dispersion in dielectric constant and dielectric loss. Activation energy and relaxation time are estimated from the Arrhenius plot. It is further shown that relaxation behaviour is altered with yttrium doping concentration. (C) 2015 AIP Publishing LLC.

Evidence for phase transitions and pseudospin phonon coupling in K-0.9(NH4)(0.1)H2AsO4

This work reports a detailed temperature dependent Raman study on the mixed crystals of K-0.9(NH4)(0.1)H2AsO4 (KADA) from 5K to 300K in the spectral range of 60-1200cm(-1), covering tetragonal to orthorhombic structural phase transition accompanied by paraelectric to ferroelectric transition at T-c* similar to 60K. Multiple phase transitions below transition temperature (Tc* similar to 60K) are marked by the appearance of new modes, splitting of existing ones as well as anomalies in the self-energy parameters (i.e. mode frequencies and damping coefficient) of the phonon modes. Temperature independent behaviour of damping coefficient and abrupt jump in the mode frequency of some of the internal vibrations of AsO4 tetrahedra as well as external vibrations clearly signal long range ferroelectric ordering and proton ordering below T-c*. In addition, we observed that temperature dependence of many prominent phonon modes diverges significantly from their normal anharmonic behaviour below T-c* suggesting potential coupling between pseudospins and phonons. (C) 2015 Author(s).

Rheological Behavior of Al-7Si-0.3Mg Alloy at Mushy State

In recent years, semisolid manufacturing has emerged as an attractive option for near net shape forming of components with aluminum alloys. In this class of processes, the key to success lies mainly in the understanding of rheological behavior of the semi-solid slurry in the temperature range between liquidus and solidus. The present study focuses on the non-Newtonian flow behavior of the pseudo plastic slurry of Al-7Si-0.3Mg alloy for a wide shear range using a high-temperature Searle-type rheometer. The rheological behavior of the slurry is studied with respect to relevant process variables and microstructural features such as shear rate, shear duration, temperature history, primary particle size, shape, and their distribution. The experiments performed are isothermal tests, continuous cooling tests, shear jump tests, and shear time tests. The continuous cooling experiments are aimed toward studying the viscosity and shear stress evolution within the slurry matrix with increasing solid fraction at a constant shear rate. Three different cooling rates are considered and their effect on flow behavior of the slurry was studied under iso-shear condition. Descending shear jump experiments are performed to understand the viscous instability of the slurry.

A 0.5-2.0 GHz injection locked oscillator cascade for parallel wideband RF spectrum sensing

An area-efficient, wideband RF frequency synthesizer, which simultaneously generates multiple local oscillator (LO) signals, is designed. It is suitable for parallel wideband RF spectrum sensing in cognitive radios. The frequency synthesizer consists of an injection locked oscillator cascade (ILOC) where all the LO signals are derived from a single reference oscillator. The ILOC is implemented in a 130-nm technology with an active area of . It generates 4 uniformly spaced LO carrier frequencies from 500 MHz to 2 GHz. This design is the first known implementation of a CMOS based ILOC for wide-band RF spectrum sensing applications.

Disappearance of electron-hole asymmetry in nanoparticles of Nd1-xCaxMnO3(x=0.6, 0.4): magnetization and electron paramagnetic resonance evidence

We study and compare magnetic and electron paramagnetic resonance behaviors of bulk and nanoparticles of Nd1-xCaxMnO3 in hole doped (x = 0.4; NCMOH) and electron doped (x = 0.6; NCMOE) samples. NCMOH in bulk form shows a complex temperature dependence of magnetization M(T), with a charge ordering transition at similar to 250 K, an antiferromagnetic (AFM) transition at similar to 150 K, and a transition to a canted AFM phase/mixed phase at similar to 80 K. Bulk NCMOE behaves quite differently with just a charge ordering transition at similar to 280 K, thus providing a striking example of the so called electron-hole asymmetry. While our magnetization data on bulk samples are consistent with the earlier reports, the new results on the nanoparticles bring out drastic effects of size reduction. They show that M(T) behaviors of the two nanosamples are essentially similar in addition to the absence of the charge order in them thus providing strong evidence for vanishing of the electron-hole asymmetry in nanomanganites. This conclusion is further corroborated by electron paramagnetic resonance studies which show that the large difference in the ``g'' values and their temperature dependences found for the two bulk samples disappears as they approach a common behavior in the corresponding nanosamples. (C) 2015 AIP Publishing LLC.