A thermodynamic study of liquid Cu-Cr alloys and metastable liquid immiscibility

he thermodynamic acitivity of chromium in liquid Cu-Cr alloys is measured in the temperature range from 1473 to 1873 K using the solid state cell: Pt, W, Cr + Cr2O3 |(Y2O3) ThO2|Cu - Cr + Cr2O3, Pt The activity of copper and the Gibbs energy of mixing of the liquid alloy are derived. Activities exhibit large positive deviations from Raoult's law. The mixing properties can be represented by a pseudo-subregular solution model in which the excess entropy has the same type of functional dependence on composition as the enthalpy of mixing: ΔGE = XCr(1 - XCr)[60880 - 18750 XCr)-- T(16.25 - 7.55 XCr)]J mol-1 Pure liquid Cu and Cr are taken as the reference states. The results predict a liquid-liquid metastable miscibility gap, with TC = 1787 (±3) K and XCr = 0.436 (±0.02), lying below the liquidus. The results obtained in this study are in general agreement with experimental information reported in the literature, but provide further refinement of the thermodynamic parameters.

Thermodynamic, kinetic and electrical switching studies on Si(15)Te(85-x)In(x) glasses: Observation of Boolchand intermediate phase

An interesting topic for quite some time is an intermediate phase observed in chalcogenide glasses, which is related to network connectivity and rigidity. This phenomenon is exhibited by Si-Te-In glasses also. It has been addressed here by carrying out detailed thermal investigations by using Alternating Differential Scanning Calorimetry technique. An effort has also been made to determine the stability of these glasses using the data obtained from different thermodynamic quantities and crystallization kinetics of these glasses. Electrical switching behavior by recording I-V characteristics and variation of switching voltages with indium composition have been studied in these glasses for phase change memory applications. (C) 2011 Elsevier Inc. All rights reserved.

Microstructure evolution and metastable phase formation in laser-ablation-deposited films of Ti5Si3 intermetallic compound

Thin films of Ti62.5Si37.5 composition were deposited by the pulsed-laser ablation technique on single-crystal Nad substrates at room temperature and on ′single-crystal′ superalloy substrates at elevated temperatures. Both vapour and liquid droplets generated by pulsed-laser ablation of the target become quenched on the substrate. Amorphization had taken place in the process of quenching of vapour-plasma as well as small liquid droplets on NaCl substrates at room temperature. In addition to the formation of Ti5Si3, a metastable fcc phase (a 0 = 0.433 nm) also forms in micron-sized large droplets as well as in the medium-sized submicron droplets. The same metastable fcc phase nucleates during deposition from the vapour state at 500°C and at 600°C on a superalloy substrate as well as during crystallization of the amorphous phase. The evolution of the metastable fcc phase in the Ti-Si system during non-equilibrium processing is reported for the first time.

Novel ATPase activity of the polyprotein intermediate, Viral Protein genome-linked-Nuclear Inclusion-a protease, of Pepper vein banding potyvirus

Potyviruses temporally regulate their protein function by polyprotein processing. Previous studies have shown that VPg (Viral Protein genome-linked) of Pepper vein banding virus interacts with the NIa-Pro (Nuclear Inclusion-a protease) domain, and modulates the kinetics of the protease. In the present study, we report for the first time that VPg harbors the Walker motifs A and B, and the presence of NIa-Pro, especially in cis (cleavage site (E191A) VPg-Pro mutant), is essential for manifestation of the ATPase activity. Mutation of Lys47 (Walker motif A) and Asp88:Glu89 (Walker motif B) to alanine in E191A VPg-Pro lead to reduced ATPase activity, confirming that this activity was inherent to VPg. We propose that potyviral VPg, established as an intrinsically disordered domain, undergoes plausible structural alterations upon interaction with globular NIa-Pro which induces the ATPase activity. (C) 2012 Elsevier Inc. All rights reserved.

Postcards from oases in the desert: phenomenology of SUSY with intermediate scales

The presence of new matter fields charged under the Standard Model gauge group at intermediate scales below the Grand Unification scale modifies the renormalization group evolution of the gauge couplings. This can in turn significantly change the running of the Minimal Supersymmetric Standard Model parameters, in particular the gaugino and the scalar masses. In the absence of new large Yukawa couplings we can parameterise all the intermediate scale models in terms of only two parameters controlling the size of the unified gauge coupling. As a consequence of the modified running, the low energy spectrum can be strongly affected with interesting phenomenological consequences. In particular, we show that scalar over gaugino mass ratios tend to increase and the regions of the parameter space with neutralino Dark Matter compatible with cosmological observations get drastically modified. Moreover, we discuss some observables that can be used to test the intermediate scale physics at the LHC in a wide class of models.

Manifestation of intermediate phase in mechanical properties: Nano-indentation studies on Ge-Te-Si bulk chalcogenide glasses

Nano-indentation studies have been undertaken on bulk Ge15Te85-xSix glasses (0 <= x <= 9), to estimate hardness, H and elastic modulus, E. It is found that E and H increase initially with the increase in the atomic percent of Si. Further, a plateau is seen in the composition dependence of E and H in the composition range 2 <= x <= 6. It is also seen that the addition of up to 2 at% Si increases the density rho of the glass considerably; however, further additions of Si lead to a near linear reduction in rho, in the range 2 <= x <= 6. Beyond x=6, rho increases again with Si content. The variation of molar volume V-m brings out a more fascinating picture. A plateau is seen in the intermediate phase suggesting that the molecular structure of the glasses is adapting to keep the count of constraints fixed in this particular phase. The observed variations in mechanical properties are associated with the Boolchand's intermediate phase in the present glassy system, in the composition range 2 <= x <= 6, suggested earlier from calorimetric and electrical switching studies. The present results reveal rather directly the existence of the intermediate phase in elastic and plastic properties of chalcogenide glasses. (C) 2012 Elsevier Ltd. All rights reserved.

Asymptotic expansions for the structural wavenumbers of isotropic and orthotropic fluid-filled circular cylindrical shells in the intermediate frequency range

We consider wavenumbers in in vacuo and fluid-filled isotropic and orthotropic shells. Using the Donnell-Mushtari (DM) theory we find compact and elegant asymptotic expansions for the wavenumbers in the intermediate frequency range, i.e., around the ring frequency. This frequency range corresponds to the frequencies where there is a rapid change in the values of bending wavenumbers and is found to exist in isotropic and orthotropic shells (in vacua and fluid-filled) for low circumferential orders n only. The same is first identified using the n=0 mode of an orthotropic shell. Following this, using the expression for the intermediate frequency, asymptotic expansions are found for other cases. Here, in order to get compact expansions we consider slight orthotropy (epsilon << 1) and light fluid loading (mu << 1). Thus, the orthotropy parameter epsilon and the fluid loading parameter mu are used as asymptotic parameters along with the non-dimensional thickness parameter beta. The methodology can be extended to any order of epsilon, only the expansions become unwieldy. The expansions are matched with the numerical solutions of the corresponding dispersion relation. The match is found to be good.

Redox regulation of protein tyrosine phosphatase 1B (PTP1B): Importance of steric and electronic effects on the unusual cyclization of the sulfenic acid intermediate to a sulfenyl amide

The redox regulation of protein tyrosine phosphatase 1B (PTP1B) via the unusual transformation of its sulfenic acid (PTP1B-SOH) to a cyclic sulfenyl amide intermediate is studied by using small molecule chemical models. These studies suggest that the sulfenic acids derived from the H2O2-mediated reactions o-amido thiophenols do not efficiently cyclize to sulfenyl amides and the sulfenic acids produced in situ can be trapped by using methyl iodide. Theoretical calculations suggest that the most stable conformer of such sulfenic acids are stabilized by n(O) -> sigma* (S-OH) orbital interactions, which force the -OH group to adopt a position trans to the S center dot center dot center dot O interaction, leading to an almost linear arrangement of the O center dot center dot center dot S-O moiety and this may be the reason for the slow cyclization of such sulfenic acids to their corresponding sulfenyl amides. On the other hand, additional substituents at the 6-position of o-amido phenylsulfenic acids that can induce steric environment and alter the electronic properties around the sulfenic acid moiety by S center dot center dot center dot N or S center dot center dot center dot O nonbonded interactions destabilize the sulfenic acids by inducing strain in the molecule. This may lead to efficient the cyclization of such sulfenic acids. This model study suggests that the amino acid residues in the close proximity of the sulfenic acid moiety in PTP1B may play an important role in the cyclization of PTP1B-SOH to produce the corresponding sulfenyl amide.

Transition and acoustic response of recirculation structures in an unconfined co-axial isothermal swirling flow

This paper reports the first observations of transition from a pre-vortex breakdown (Pre-VB) flowreversal to a fully developed central toroidal recirculation zone in a non-reacting, double-concentric swirling jet configuration and its response to longitudinal acoustic excitation. This transition proceeds with the formation of two intermediate, critical flow regimes. First, a partially penetrated vortex breakdown bubble (VBB) is formed that indicates the first occurrence of an enclosed structure as the centre jet penetration is suppressed by the growing outer roll-up eddy; resulting in an opposed flow stagnation region. Second, a metastable transition structure is formed that marks the collapse of inner mixing vortices. In this study, the time-averaged topological changes in the coherent recirculation structures are discussed based on the non-dimensional modified Rossby number (Ro(m)) which appears to describe the spreading of the zone of swirl influence in different flow regimes. Further, the time-mean global acoustic response of pre-VB and VBB is measured as a function of pulsing frequency using the relative aerodynamic blockage factor (i.e., maximum radial width of the inner recirculation zone). It is observed that all flow modes except VBB are structurally unstable as they exhibit severe transverse radial shrinkage (similar to 20%) at the burner Helmholtz resonant modes (100-110 Hz). In contrast, all flow regimes show positional instability as seen by the large-scale, asymmetric spatial shifting of the vortex core centres. Finally, the mixing transfer function M (f) and magnitude squared coherence lambda(2)(f) analysis is presented to determine the natural couplingmodes of the system dynamic parameters (u', p'), i.e., local acoustic response. It is seen that the pre-VB flow mode exhibits a narrow-band, low pass filter behavior with a linear response window of 100-105 Hz. However, in the VBB structure, presence of critical regions such as the opposed flow stagnation region alters the linearity range with the structure showing a response even at higher pulsing frequencies (100-300 Hz). (C) 2013 AIP Publishing LLC.

Metastable morphotropic phase boundary state in the multiferroic BiFeO3-PbTiO3

Temperature-time study of the magnetoelectric multiferroic (1-x)BiFeO3-(x)PbTiO3 by x-ray and electron diffraction on the reported morphotropic phase boundary (MPB) compositions revealed that this MPB does not correspond to the equilibrium state. The MPB like state is rather of metastable nature and arise due to kinetic arrest of metastable rhombohedral (R3c) phase, along with the equilibrium tetragonal (P4mm) phase. The life time of the metastable R3c nuclei is very sensitive to composition and temperature, and nearly diverges at x -> 0.27. The MPB like state appears only if the system is cooled before the metastable R3c nuclei could vanish. These findings resolve the long standing controversy with regard to seemingly erratic phase formation behaviour reported by different groups and provides a rational basis for developing genuine equilibrium MPB compositions in this system for better piezoelectric properties. (C) 2013 AIP Publishing LLC.

Solid-solid collapse transition in a two dimensional model molecular system

Solid-solid collapse transition in open framework structures is ubiquitous in nature. The real difficulty in understanding detailed microscopic aspects of such transitions in molecular systems arises from the interplay between different energy and length scales involved in molecular systems, often mediated through a solvent. In this work we employ Monte-Carlo simulation to study the collapse transition in a model molecular system interacting via both isotropic as well as anisotropic interactions having different length and energy scales. The model we use is known as Mercedes-Benz (MB), which, for a specific set of parameters, sustains two solid phases: honeycomb and oblique. In order to study the temperature induced collapse transition, we start with a metastable honeycomb solid and induce transition by increasing temperature. High density oblique solid so formed has two characteristic length scales corresponding to isotropic and anisotropic parts of interaction potential. Contrary to the common belief and classical nucleation theory, interestingly, we find linear strip-like nucleating clusters having significantly different order and average coordination number than the bulk stable phase. In the early stage of growth, the cluster grows as a linear strip, followed by branched and ring-like strips. The geometry of growing cluster is a consequence of the delicate balance between two types of interactions, which enables the dominance of stabilizing energy over destabilizing surface energy. The nucleus of stable oblique phase is wetted by intermediate order particles, which minimizes the surface free energy. In the case of pressure induced transition at low temperature the collapsed state is a disordered solid. The disordered solid phase has diverse local quasi-stable structures along with oblique-solid like domains. (C) 2013 AIP Publishing LLC.

Evidence of an intermediate phase in a quaternary Ag bearing telluride glass system using alternating DSC

Alternating Differential Scanning Calorimetric (ADSC) studies on quaternary Ge15Te80-xIn5Agx glasses show the non-reversing enthalpy (Delta H-NR) at T-g to exhibit a broad global minimum in the 8% <= x <= 16% range of Ag, an observation that is taken evidence for existence of an Intermediate Phase (IP) in that range. Glasses at x < 8% are in the flexible phase while those at x > 16% in the stressed-rigid phase. The nature of crystalline phases formed upon crystallization of bulk glasses are elucidated by XRD studies, and reveal presence of Te, GeTe, Ag8GeTe6, AgTe, In2Te3 and In4Te3 phases. These experiments also reveal that the fraction of Ag- bearing phases increases while those of Te- bearing ones decreases with increasing x, suggesting progressive replacement of Te-Te bonds by Ag-Te bonds. (C) 2013 Elsevier Ltd. All rights reserved.

Stabilization of metastable tetragonal phase in a rhombohedral magnetoelectric multiferroic BiFeO3-PbTiO3

The phase formation behaviour of the magnetoelectric multiferroic 0.8BiFeO(3)-0.2PbTiO(3) was studied as a function of heat treatment at different temperatures of a sol-gel derived powder. While under ordinary synthesis conditions this composition exhibits antiferromagnetic ordering and a rhombohedral structure; the sol-gel-enabled low-temperature synthesis could stabilize a tetragonal metastable phase along with the stable rhombohedral phase, mimicking a morphotropic phase boundary state. The phase coexistence state exhibits relatively enhanced ferromagnetic correlation. The same system with a relatively higher PbTiO3 concentration, 0.65BiFeO(3)-0.35PbTiO(3), on the other hand, exhibits a rhombohedral metastable phase. These results suggest that the occurrence of metastable phases is a very common feature in the BiFeO3-PbTiO3 magnetoelectric ferroelectric system and that it affects the ferroelectric and magnetic properties of system quite remarkably.

Investigation on the Sr-doped ceria Ce1-xSrO2-delta (x=0.05-0.2) as an electrolyte for intermediate temperature SOFC

The effect of Sr doping in CeO2 for its use as solid electrolytes for intermediate temperature solid oxide fuel cells (IT-SOFCs) has been explored here. Ce1-xSrxO2-delta (x = 0.05-0.2) are successfully synthesized by citrate-complexation method. XRD, Raman, FT-IR, FE-SEM/EDX and electrochemical impedance spectra are used for structural and electrical characterizations. The formation of well crystalline cubic fluorite structured solid solution is observed for x = 0.05 based on XRD and Raman spectra. For compositions i.e., x > 0.05, however, a secondary phase of SrCeO3 is confirmed by the peak at 342 cm(-1) in Raman spectra. Although the oxygen ion conductivity was found to decrease with increase in x, based on ac-impedance studies, conductivity of Ce0.95Sr0.05O2-delta was found to be higher than of Ce0.95Gd0.1O2-delta and Ce0.8Gd0.2O2-delta. The decrease in conductivity of Ce1-xSrxO2-delta with increasing dopant concentration is ascribed to formation of impurity phase SrCeO3 as well as the formation of neutral associated pairs, Se `' Ce V-o. The activation energies are found to be 0.77, 0.83, 0.85 and 0.90 eV for x = 0.05, 0.1, 0.15 and 0.20, respectively. (C) 2014 Elsevier B.V. All rights reserved.