Effect of hydrogen on the yielding behavior and shear transformation zone volume in metallic glass ribbons

The effect of hydrogen (H) charging on the shear yield strength (tau(max)) and shear transformation zone volume (Omega) of Ni-Nb-Zr metallic glass ribbons, with varying Zr content, were studied through the first pop-in loads during nanoindentation. Weight gain measurements after H charging and desorption studies were utilized to identify how the total H absorbed during charging is partitioned into mobile and immobile (or trapped) parts. These, in turn, indicate the significant role of H mobility in the amorphous structure on the yielding behavior. In high-Zr alloys, tau(max) increases significantly whereas Omega decreases. In low-Zr alloys, a slight decrease in tau(max) and increase in Omega were noted. These experimental observations are rationalized in terms of the mobility of the absorbed H in the amorphous structure and the possible role of it in the shear transformation zone dynamics during deformation of the metallic glass. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Polymorphism and Phase Transformation Behavior of Solid Forms of 4-Amino-3,5-dinitrobenzamide

We report the preparation, analysis, and phase transformation behavior of polymorphs and the hydrate of 4-amino-3,5-dinitrobenzamide. The compound crystallizes in four different polymorphic forms, Form I (monoclinic, P2(1)/n), Form II (orthorhombic, Pbca), Form III (monoclinic, P2(1)/c), and Form IV (monoclinic, P2(1)/c). Interestingly, a hydrate (triclinic, P (1) over bar) of the compound is also discovered during the systematic identification of the polymorphs. Analysis of the polymorphs has been investigated using hot stage microscopy, differential scanning calorimetry, in situ variable-temperature powder X-ray diffraction, and single-crystal X-ray diffraction. On heating, all of the solid forms convert into Form I irreversibly, and on further heating, melting is observed. In situ single-crystal X-ray diffraction studies revealed that Form II transforms to Form I above 175 degrees C via single-crystal-to-single-crystal transformation. The hydrate, on heating, undergoes a double phase transition, first to Form III upon losing water in a single-crystal-to-single-crystal fashion and then to a more stable polymorph Form I on further heating. Thermal analysis leads to the conclusion that Form II appears to be the most stable phase at ambient conditions, whereas Form I is more stable at higher temperature.

PolyGLoT: A Polyhedral Loop Transformation Framework for a Graphical Dataflow Language

Polyhedral techniques for program transformation are now used in several proprietary and open source compilers. However, most of the research on polyhedral compilation has focused on imperative languages such as C, where the computation is specified in terms of statements with zero or more nested loops and other control structures around them. Graphical dataflow languages, where there is no notion of statements or a schedule specifying their relative execution order, have so far not been studied using a powerful transformation or optimization approach. The execution semantics and referential transparency of dataflow languages impose a different set of challenges. In this paper, we attempt to bridge this gap by presenting techniques that can be used to extract polyhedral representation from dataflow programs and to synthesize them from their equivalent polyhedral representation. We then describe PolyGLoT, a framework for automatic transformation of dataflow programs which we built using our techniques and other popular research tools such as Clan and Pluto. For the purpose of experimental evaluation, we used our tools to compile LabVIEW, one of the most widely used dataflow programming languages. Results show that dataflow programs transformed using our framework are able to outperform those compiled otherwise by up to a factor of seventeen, with a mean speed-up of 2.30x while running on an 8-core Intel system.

Phase transformation of ZrO2:Tb3+ nanophosphor: Color tunable photoluminescence and photocatalytic activities

The current study involves synthesis of a series of Tb3+ doped ZrO2 nanophosphors by solution combustion method using oxalyl dihydrazide as fuel. The as-formed ZrO2:Tb3+ nanophosphors having different concentrations of Tb3+ (1-11 mol%) were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Visible spectroscopic techniques and the materials were subjected to photoluminescence and photocatalytic dye decolorization studies. The PXRD analysis indicates the formation of tetragonal symmetry up to 5 mol% concentration of Tb3+. Further increase in Tb3+ concentration has lead to cubic phase formation and the same was confirmed by Rietveld refinement analysis. SEM images revealed that material was highly porous in nature comprising of large voids and cracks with irregular morphology. TEM and SAED images clearly confirm the formation of high quality tetragonal nanocrystals. The emissive properties of nanophosphors were found to be dependent on Tb3+ dopant concentration. The green emission of the material was turned to white emission with the increase of Tb3+ ion concentration. The photocatalytic activities of these nanophosphors were probed for the decolorization of Congo red under UV and Sunlight irradiation. All the photocatalysts showed enhanced activity under UV light compared to Sunlight. The photocatalyst with 7 mol% Tb3+ showed enhanced activity attributed to effective separation of charge carriers due to phase transformation from tetragonal to cubic. The influence of crystallite size and PL on charge carrier trapping-recombination dynamics was investigated. The study successfully demonstrates synthesis of tetragonal and cubic ZrO2:Tb3+ green nanophosphors with superior photoluminescence and photocatalytic activities. (C) 2014 Elsevier B.V. All rights reserved.

Discrete Vortex Method-Based Model for Ground-Effect Studies

A discrete vortex method-based model has been proposed for two-dimensional/three-dimensional ground-effect prediction. The model merely requires two-dimensional sectional aerodynamics in free flight. This free-flight data can be obtained either from experiments or a high-fidelity computational fluid dynamics solver. The first step of this two-step model involves a constrained optimization procedure that modifies the vortex distribution on the camber line as obtained from a discrete vortex method to match the free-flight data from experiments/computational fluid dynamics. In the second step, the vortex distribution thus obtained is further modified to account for the presence of the ground plane within a discrete vortex method-based framework. Whereas the predictability of the lift appears as a natural extension, the drag predictability within a potential flow framework is achieved through the introduction of what are referred to as drag panels. The need for the use of the generalized Kutta-Joukowski theorem is emphasized. The extension of the model to three dimensions is by the way of using the numerical lifting-line theory that allows for wing sweep. The model is extensively validated for both two-dimensional and three-dimensional ground-effect studies. The work also demonstrates the ability of the model to predict lift and drag coefficients of a high-lift wing in ground effect to about 2 and 8% accuracy, respectively, as compared to the results obtained using a Reynolds-averaged Navier-Stokes solver involving grids with several million volumes. The model shows a lot of promise in design, particularly during the early phase.

Analogous stress and electric field driven structural transformation and decrease in polarization coherence on poling around the morphotropic phase boundary in BiScO3-PbTiO3

The nature of the stress and electric field driven structural and microstructural transformations in the morphotropic phase boundary (MPB) compositions of the high Curie point piezoelectric system BiScO3-PbTiO3 has been examined by ex situ based techniques. Using a powder poling technique, which is based on the concept of exploiting the irreversible structural change that occurs after the application of a strong electric field and stress independently, it was possible to ascertain that both moderate stress and electric field induce identical structural transformation-a fraction of the monoclinic phase transforms irreversibly to the tetragonal phase. Moreover, analysis of the dielectric response before and after poling revealed a counterintuitive phenomenon of poling induced decrease in the spatial coherence of polarization for compositions around the MPB and not so for compositions far away from the MPB range. Exploiting the greater sensitivity of this technique, we demonstrate that the criticality associated with the interferroelectric transition spans a wider composition range than what is conventionally reported in the literature based on bulk x-ray/neutron powder diffraction techniques.

Linear Index Coding and Representable Discrete Polymatroids

Discrete polymatroids are the multi-set analogue of matroids. In this paper, we explore the connections between linear index coding and representable discrete polymatroids. The index coding problem involves a sender which generates a set of messages X = {x(1), x(2), ... x(k)} and a set of receivers R which demand messages. A receiver R is an element of R is specified by the tuple (x, H) where x. X is the message demanded by R and H subset of X \textbackslash {x} is the side information possessed by R. It is first shown that a linear solution to an index coding problem exists if and only if there exists a representable discrete polymatroid satisfying certain conditions which are determined by the index coding problem considered. El Rouayheb et. al. showed that the problem of finding a multi-linear representation for a matroid can be reduced to finding a perfect linear index coding solution for an index coding problem obtained from that matroid. Multi-linear representation of a matroid can be viewed as a special case of representation of an appropriate discrete polymatroid. We generalize the result of El Rouayheb et. al. by showing that the problem of finding a representation for a discrete polymatroid can be reduced to finding a perfect linear index coding solution for an index coding problem obtained from that discrete polymatroid.

High Proton Mobility, Solvent Induced Single Crystal to Single Crystal Structural Transformation, and Related Studies on a Family of Compounds Formed from Mn-3 Oxo-Clusters

The reaction between 4,4'-sulfonyldibenzoic acid (H(2)SDBA) and manganese under mild conditions resulted in the isolation of two new three-dimensional compounds, Mn-4(C14H8O6S)(4)(DMA)(2)]center dot 3DMA, I, and Mn-3(C14H8O6S)(3)(DMA)(2)(MeOH)]center dot DMA, IIa. Both structures have Mn-3 trimer oxo cluster units. While the Mn-3 oxoclusters are connected through octahedral manganese forming one-dimensional Mn-O-Mn chains in I, the Mn-3 units are isolated in IIa. The SDBA units connect the Mn-O-Mn chains and the Mn-3 clusters giving rise to the three-dimensional structure. Both compounds have coordinated and free solvent molecules. In IIa, two different solvent molecules are coordinated, of which one solvent can be reversibly exchanged by a variety of other similar solvents via a solvent-mediated single crystal to single crystal (SCSC) transformation. The free lattice DMA solvent molecules in I can be exchanged by water molecules resulting in hydrophilic channels. Proton conductivity studies on I reveals a high proton mobility with conductivity values of similar to 0.87 x 10(-3) Omega(-1) cm(-1) at 34 degrees C and 98% RH, which is comparable to some of the good proton conductivity values observed in inorganic coordination polymers. We have also shown structural transformation of I to IIa through a possible dissolution and recrystallization pathway. In addition, both I and IIa appear to transform to two other manganese compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5) and H3O](2)Mn-7(mu 3-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8) under suitable reaction conditions. We have partially substituted Co in place of Mn in the Mn-3 trimer clusters forming CoMn2(C14H8O6S)(3)(DMA)(2)(EtOH)]center dot DMA, III, a structure that is closely related to IIa. All the compounds reveal antiferromagnetic behavior. On heating, the cobalt substituted phase (compound III) forms a CoMn2O4 spinel phase with particle sizes in the nanometer range.

Discrete-Rate Adaptation and Selection in Energy Harvesting Wireless Systems

In a system with energy harvesting (EH) nodes, the design focus shifts from minimizing energy consumption by infrequently transmitting less information to making the best use of available energy to efficiently deliver data while adhering to the fundamental energy neutrality constraint. We address the problem of maximizing the throughput of a system consisting of rate-adaptive EH nodes that transmit to a destination. Unlike related literature, we focus on the practically important discrete-rate adaptation model. First, for a single EH node, we propose a discrete-rate adaptation rule and prove its optimality for a general class of stationary and ergodic EH and fading processes. We then study a general system with multiple EH nodes in which one is opportunistically selected to transmit. We first derive a novel and throughput-optimal joint selection and rate adaptation rule (TOJSRA) when the nodes are subject to a weaker average power constraint. We then propose a novel rule for a multi-EH node system that is based on TOJSRA, and we prove its optimality for stationary and ergodic EH and fading processes. We also model the various energy overheads of the EH nodes and characterize their effect on the adaptation policy and the system throughput.

Sphere to ring morphological transformation in drying nanofluid droplets in a contact-free environment

Understanding the transients of buckling in drying colloidal suspensions is pivotal for producing new functional microstructures with tunable morphologies. Here, we report first observations and elucidate the buckling instability induced morphological transition (sphere to ring structure) in an acoustically levitated, heated nanosuspension droplet using dynamic energy balance. Droplet deformation featuring the formation of symmetric cavities is initiated by capillary pressure that is two to three orders of magnitude greater than the acoustic radiation pressure, thus indicating that the standing pressure field has no influence on the buckling front kinetics. With an increase in heat flux, the growth rate of surface cavities and their post-buckled volume increase while the buckling time period reduces, thereby altering the buckling pathway and resulting in distinct precipitate structures. However, irrespective of the heating rate, the volumetric droplet deformation exhibits a linear time dependence and the droplet vaporization is observed to deviate from the classical D-2-law.

Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

Self-Assembled Discrete Molecules for Sensing Nitroaromatics

Efficient sensing of trace amount nitroaromatic (NAC) explosives has become a major research focus in recent time due to concerns over national security as well as their role as environment pollutants. NO2-containing electron-deficient aromatic compounds, such as picric acid (PA), trinitrotoluene (TNT), and dinitrotoluene (DNT), are the common constituents of many commercially available chemical explosives. In this article, we have summarized our recent developments on the rational design of electron-rich self-assembled discrete molecular sensors and their efficacy in sensing nitroaromatics both in solution as well as in vapor phase. Several p-electron-rich fluorescent metallacycles (squares, rectangles, and tweezers/pincers) and metallacages (trigonal and tetragonal prisms) have been synthesized by means of metal-ligand coordination-bonding interactions, with enough internal space to accommodate electron-deficient nitroaromatics at the molecular level by multiple supramolecular interactions. Such interactions subsequently result in the detectable fluorescence quenching of sensors even in the presence of trace quantities of nitroaromatics. The fascinating sensing characteristics of molecular architectures discussed in this article may enable future development of improved sensors for nitroaromatic explosives.

Copper-Catalyzed Direct Transformation of Secondary Allylic and Benzylic Alcohols into Azides and Amides: An Efficient Utility of Azide as a Nitrogen Source

A mild and convenient method for the synthesis of amides has been explored by using secondary alcohols, Cu(ClO4)(2)6H(2)O as a catalyst, and trimethylsilyl azide (TMSN3) as a nitrogen source in the presence of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) at ambient temperature. This method has been successfully adapted to the preparation of azides directly from their corresponding alcohols and offers excellent chemoselectivity in the formation of -halo azides and the azidation of allylic alcohols in the presence of a benzyl alcohol moiety. In addition, this strategy provides an opportunity to synthesize azides that can serve as precursors to -amino acids.

Girsanov Transformation-Based Reliability Modeling and Testing of Actively Controlled Structures

The problem of estimation of the time-variant reliability of actively controlled structural dynamical systems under stochastic excitations is considered. Monte Carlo simulations, reinforced with Girsanov transformation-based sampling variance reduction, are used to tackle the problem. In this approach, the external excitations are biased by an additional artificial control force. The conflicting objectives of the two control forces-one designed to reduce structural responses and the other to promote limit-state violations (but to reduce sampling variance)-are noted. The control for variance reduction is fashioned after design-point oscillations based on a first-order reliability method. It is shown that for structures that are amenable to laboratory testing, the reliability can be estimated experimentally with reduced testing times by devising a procedure based on the ideas of the Girsanov transformation. Illustrative examples include studies on a building frame with a magnetorheologic damper-based isolation system subject to nonstationary random earthquake excitations. (C) 2014 American Society of Civil Engineers.

Alternative Formulation of the Discrete Linear Quadratic Regulator (DLQR)

In this paper, an alternative apriori and aposteriori formulation has been derived for the discrete linear quadratic regulator (DLQR) in a manner analogous to that used in the discrete Kalman filter. It has been shown that the formulation seamlessly fits into the available formulation of the DLQR and the equivalent terms in the existing formulation and the proposed formulation have been identified. Thereafter, the significance of this alternative formulation has been interpreted in terms of the sensitivity of the controller performances to any changes in the states or to changes in the control inputs. The implications of this alternative formulation to adaptive controller tuning have also been discussed.