Synthesis of a mixed-metal spinel, NiMn2O4, through site-selective substitution in MOF, (NiMn2){C6H3(COO)(3)}(2)]: synthesis, structure and magnetic studies

A mixed-metal metal-organic framework (MOF) compound NiMn2{C6H3(COO)(3)}(2)], I, is prepared hydrothermally by replacing one of the octahedral Mn2+ ions in Mn-3{C6H3(COO)(3)}(2)] by Ni2+ ions. Magnetic studies on I suggest antiferromagnetic interactions with weak canted antiferromagnetism below 8 K. On heating in flowing air I transforms to NiMn2O4 spinel at low temperature (T < 400 degrees C). The thermal decomposition of I at different temperatures results in NiMn2O4 with particle sizes in the nano regime. The nanoparticle nature of NiMn2O4 was confirmed using PXRD and TEM studies. Magnetic studies on the nanoparticles of NiMn2O4 indicate ferrimagnetism. The transition temperature of NiMn2O4 nanoparticles exhibits a direct correlation with the particle size. This study highlights the usefulness of MOF compound as a single-source precursor for the preparation of important ceramic oxides with better control on the stoichiometry and particle size.

Tensile behavior of a free-standing Pt-aluminide (PtAl) bond coat

The tensile behavior of a high activity stand-alone Pt-aluminide (PtAl) bond coat was evaluated by the micro-tensile test method at various temperatures (room temperature to 1100 degrees C) and strain rates (10(-5) s(-1)-10(-1) s(-1).) At all strain rates, the stress strain behavior of the stand-alone coating was significantly affected by the variation in temperature. The stress strain response was linear, indicating brittle behavior, at temperatures below the brittle ductile transition temperature (BDTT). The coating exhibited appreciable ductility (up to 2%) above the BDTT. The strength (both yield stress and ultimate tensile strength) of the coating decreased and its ductility increased with increasing temperature above the BDTT. The tensile behavior of the coating was sensitive to strain rate in the ductile regime, with its strength increasing with increasing strain rate at any given temperature. The BDTT of the coating was found to increase with increasing with increasing strain rate. The coating exhibited two distinct mechanisms of deformation above the BDTT. The transition temperature for the change of deformation mechanism also increased with increasing strain rate. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Structural and relaxor characteristics of Ca0.18Sr0.226Ba0.594Nb2O6

Polycrystalline Ca0.18Sr0.226Ba0.594Nb2O6 (CSBN18) was synthesized via the solid-state reaction route. X-ray structural studies confirmed it belonged to the tetragonal tungsten bronze family. Rietveld refinement of the X-ray data has been carried out for CSBN18 where the atomic positions and site occupancy factors for A-sites have been determined. The dielectric properties of CSBN18 ceramic were studied as a function of temperature in the 100 Hz - 1 MHz frequency range. The dielectric relaxation followed the Vogel-Fulcher relation wherein E-a = 37.4 meV; T-f = 131.5 degrees C and omega(0) = 4.31 x 10(9) rad s(-1). A high pyroelectric coefficient of similar to 250 mu C m(-2).K was obtained around the transition temperature (similar to 150 degrees C). This is significantly higher than that reported for polycrystalline SrxBa1-xNb2O6 (SBN). However, the piezoelectric coefficient (d(33)) of the title composition was as low as 6 pC N-1.

Fermions in synthetic non-Abelian gauge potentials: rashbon condensates to novel Hamiltonians

Recent advances in the generation of synthetic gauge fields in cold atomic systems have stimulated interest in the physics of interacting bosons and fermions in them. In this paper, we discuss interacting two-component fermionic systems in uniform non-Abelian gauge fields that produce a spin-orbit interaction and uniform spin potentials. Two classes of gauge fields discussed include those that produce a Rashba spin-orbit interaction and the type of gauge fields (SM gauge fields) obtained in experiments by the Shanxi and MIT groups. For high symmetry Rashba gauge fields, a two-particle bound state exists even for a vanishingly small attractive interaction described by a scattering length. Upon increasing the strength of a Rashba gauge field, a finite density of weakly interacting fermions undergoes a crossover from a BCS like ground state to a BEC state of a new kind of boson called the rashbon whose properties are determined solely by the gauge field and not by the interaction between the fermions. The rashbon Bose-Einstein condensate (RBEC) is a quite intriguing state with the rashbon-rashbon interactions being independent of the fermion-fermion interactions (scattering length). Furthermore, we show that the RBEC has a transition temperature of the order of the Fermi temperature, suggesting routes to enhance the transition temperatures of weakly interacting superfluids by tuning the spin-orbit coupling. For the SM gauge fields, we show that in a regime of parameters, a pair of particles with finite centre-of-mass momentum is the most strongly bound. In other regimes of centre-of-mass momenta, there is no two-body bound state, but a resonance like feature appears in the scattering continuum. In the many-body setting, this results in flow enhanced pairing. Also, strongly interacting normal states utilizing the scattering resonance can be created opening the possibility of studying properties of helical Fermi liquids. This paper contains a general discussion of the physics of Feshbach resonance in a non-Abelian gauge field, where several novel features such as centre-of-mass-momentum-dependent effective interactions are shown. It is also shown that a uniform non-Abelian gauge field in conjunction with a spatial potential can be used to generate novel Hamiltonians; we discuss an explicit example of the generation of a monopole Hamiltonian.

Multiwalled-carbon-nanotube-induced miscibility in near-critical PS/PVME blends: assessment through concentration fluctuations and segmental relaxation

The effects of multiwalled carbon nanotubes (MWNTs) on the concentration fluctuations, interfacial driven elasticity, phase morphology, and local segmental dynamics of chains for near-critical compositions of polystyrene/poly(vinyl to methyl ether) (PS/PVME) blends were systematically investigated using dynamic shear rheology and dielectric spectroscopy. The contribution of the correlation length (xi) of the concentration fluctuations to the evolving stresses was monitored in situ to probe the different stages of demixing in the blends. The classical upturn in the dynamic moduli was taken as the rheological demixing temperature (T-rheo), which was also observed to be in close agreement with those obtained using concentration fluctuation variance, <(delta phi)(2)>, versus temperature curves. Further, Fredrickson and Larson's approach involving the mean-field approximation and the double-reptation self-concentration (DRSC) model was employed to evaluate the spinodal decomposition temperature (T-s). Interestingly, the values of both T-rheo and T-s shifted upward in the blends in the presence of MWNTs, manifesting in molecular-level miscibility. These phenomenal changes were further observed to be a function of the concentration of MWNTs. The evolution of morphology as a function of temperature was studied using polarized optical microscopy (POM). It was observed that PVME, which evolved as an interconnected network during the early stages of demixing, coarsened into a matrix-droplet morphology in the late stages. The preferential wetting of PVME onto MWNTs as a result of physicochemical interactions retained the interconnected network of PVME for longer time scales, as supported by POM and atomic force microscopy (AFM) images. Microscopic heterogeneity in macroscopically miscible systems was studied by dielectric relaxation spectroscopy. The slowing of segmental relaxations in PVME was observed in the presence of both ``frozen'' PS and MWNTs interestingly at temperatures much below the calorimetric glass transition temperature (T-g). This phenomenon was observed to be local rather than global and was addressed by monitoring the evolution of the relaxation spectra near and above the demixing temperature.

Structure-property correlation in BaO-TiO2-B2O3 glasses: glass stability, optical, hydrophobic, and dielectric properties

Glasses in the x(BaO-TiO2)-B2O3 (x = 0.25, 0.5, 0.75, and 1 mol.) system were fabricated via the conventional melt-quenching technique. Thermal stability and glass-forming ability as determined by differential thermal analysis (DTA) were found to increase with increasing BaO-TiO2 (BT) content. However, there was no noticeable change in the glass transition temperature (T-g). This was attributed to the active participation of TiO2 in the network formation especially at higher BT contents via the conversion of the TiO6 structural units into TiO4 units, which increased the connectivity and resulted in an increase in crystallization temperature. Dielectric and optical properties at room temperature were studied for all the glasses under investigation. Interestingly, these glasses were found to be hydrophobic. The results obtained were correlated with different structural units and their connectivity in the glasses.

Glycidyl azide polymer crosslinked through triazoles by click chemistry: curing, mechanical and thermal properties

Glycidyl azide polymer (GAP) was cured through click chemistry by reaction of the azide group with bispropargyl succinate (BPS) through a 1,3-dipolar cycloaddition reaction to form 1,2,3-triazole network. The properties of GAP-based triazole networks are compared with the urethane cured GAP-systems. The glass transition temperature (T-g), tensile strength, and modulus of the system increased with crosslink density, controlled by the azide to propargyl ratio. The triazole incorporation has a higher T-g in comparison to the GAP-urethane system (T-g-20 degrees C) and the networks exhibit biphasic transitions at 61 and 88 degrees C. The triazole curing was studied using Differential Scanning Calorimetry (DSC) and the related kinetic parameters were helpful for predicting the cure profile at a given temperature. Density functional theory (DFT)-based theoretical calculations implied marginal preference for 1,5-addition over 1,4-addition for the cycloaddition between azide and propargyl group. Thermogravimetic analysis (TG) showed better thermal stability for the GAP-triazole and the mechanism of decomposition was elucidated using pyrolysis GC-MS studies. The higher heat of exothermic decomposition of triazole adduct (418kJmol(-1)) against that of azide (317kJmol(-1)) and better mechanical properties of the GAP-triazole renders it a better propellant binder than the GAP-urethane system.

Crystallographic texture and microstructure evolution during hot compression of Ti-6Al-4V-0.1B alloy in the (alpha plus beta)-regime

Microstructure and texture are known to undergo drastic modifications due to trace hypoeutectic boron addition (similar to 0.1wt.%) for various titanium alloys e.g. Ti-6Al-4V. The deformation behaviour of such an alloy Ti-6Al-4V-0.1B is investigated in the (+) phase field and compared against that of the base alloy Ti-6Al-4V studied under selfsame conditions. The deformation microstructures for the two alloys display bending and kinking of lamellae in near and softening via globularization of lamella in near phase regimes, respectively. The transition temperature at which pure slip based deformation changes to softening is lower for the boron added alloy. The presence of TiB particles is largely held attributable for the early softening of Ti-6Al-4V-0.1B alloy. The compression texture of both the alloys carry signature of pure phase defamation at lower temperature and phase transformation near the transus temperature. Texture is influenced by a complex interplay of the deformation and transformation processes in the intermediate temperature range. The contribution from phase transformation is prominent for Ti-6Al-4V-0.1B alloy at comparatively lower temperature.

Cross-Linked, Biodegradable, Cytocompatible Salicylic Acid Based Polyesters for Localized, Sustained Delivery of Salicylic Acid: An In Vitro Study

In order to suppress chronic inflammation while supporting cell proliferation, there has been a continuous surge toward development of polymers with the intention of delivering anti-inflammatory molecules in a sustained manner. In the above backdrop, we report the synthesis of a novel, stable, cross-linked polyester with salicylic acid (SA) incorporated in the polymeric backbone and propose a simple synthesis route by melt condensation. The as-synthesized polymer was hydrophobic with a glass transition temperature of 1 degrees C, which increases to 17 degrees C upon curing. The combination of NMR and FT-IR spectral techniques established the ester linkages in the as-synthesized SA-based polyester. The pH-dependent degradation rate and the rate of release of salicylic acid from the as-synthesized SA-based polymer were studied at physiological conditions in vitro. The polyester underwent surface erosion and exhibited linear degradation kinetics in which a change in degradation rate is observed after 4-10 days and 24% mass loss was recorded after 4 months at 37 degrees C and pH 7.4. The delivery of salicylic acid also showed a similar change in slopes, with a sustained release rate of 3.5% in 4 months. The cytocompatibility studies of these polyesters were carried out with C2C12 murine myoblast cells using techniques like MTT assay and flow cytometry. Our results strongly suggest that SA-based polyester supports cell proliferation for 3 days in culture and do not cause cell death (<7%), as quantified by propidium iodide (PI) stained cells. Hence, these polyesters can be used as implant materials for localized, sustained delivery of salicylic acid and have applications in adjuvant cancer therapy, chronic wound healing, and as an alternative to commercially available polymers like poly(lactic acid) and poly(glycolic acid) or their copolymers.

Micromechanisms of fracture and strengthening in free-standing Pt-aluminide bond coats under tensile loading

Free-standing Pt-aluminide (PtAl) bond coats exhibit a linear stress strain response under tensile loading and undergo brittle cleavage fracture at temperatures below the brittle-to-ductile transition temperature (BDTT). Above the BDTT, these coatings show yielding and fail in a ductile manner. In this paper, the various micromechanisms affecting the tensile fracture stress (FS) below the BDTT and yield strength (YS) above the BDTT in a PtAl bond coat have been ascertained and quantified at various temperatures. The micromechanisms have been identified by carrying out microtensile testing of stand-alone PtAl coating specimens containing different levels of Pt at temperatures between room temperature and 1100 degrees C and correlation of the corresponding fracture mechanisms with the deformation substructure in the coating. An important aspect of the influence of Pt on the tensile behavior, slip characteristics, FS/YS and BDTT in the PtAl coating has also been examined. The addition of Pt enhances the FS of the coating by Pt solid solution strengthening and imparts a concomitant increase in fracture toughness and yet causes a significant increase in the BDTT of the coating. Published by Elsevier Ltd. on behalf of Acta Materialia Inc.

Fermionic superfluid from a bilayer band insulator in an optical lattice

We propose a model to realize a fermionic superfluid state in an optical lattice circumventing the cooling problem. Our proposal exploits the idea of tuning the interaction in a characteristically low-entropy state, a band insulator in an optical bilayer system, to obtain a superfluid. By performing a detailed analysis of the model including fluctuations and augmented by a variational quantum Monte Carlo calculation of the ground state, we show that the superfluid state obtained has a high transition temperature of the order of the hopping energy. Our system is designed to suppress other competing orders such as a charge density wave. We suggest a laboratory realization of this model via an orthogonally shaken optical lattice bilayer.

Effect Of Mo Doping On The Electrical Properties Of VO2 Phase

Solution combustion synthesis technique was adopted to synthesize V2O5, and Mo doped phases, The as-synthesized V2O5, has been reduced by a novel reduction technique to form VO2 typephase. The monophasic nature of the samples as revealed by XRD data and systematic shift in peak position indicated solid solubility up to 2 at % of Mo in VO2 lattice. The crystallite size was found to similar to 40 nm. Particle size measurement carried out using Transmission electron microscope ( TEM) agreed with XRD experiments. Scanning electron microscope revealed the morphology of the particles to be plate like and bimodal. Variation in the metal- insulator transition temperature as a function of doping was investigated by 4-probe electrical resistivity measurement on sintered ceramics.

Non-equilibrium segmental dynamics driven by multiwall carbon nanotubes in PS/PVME blends

The present paper discusses the effect of multiwall carbon nanotubes (MWNTs) on the structural relaxation and the intermolecular cooperativity in dynamically asymmetric blends of PS/PVME (polystyrene/poly(vinyl methyl ether)). The temperature regime where chain connectivity effects dominate the thermodynamic concentration fluctuation (T/T-g > 0.75, T-g is the glass transition temperature of the blends) was studied using dielectric spectroscopy (DS). Interestingly, in the blends with MWNTs a bimodal distribution of relaxation was obtained in the loss modulus spectra. This plausibly is due to different environments experienced by the faster component (PVME) in the presence of MWNTs. The segmental dynamics of PVME was observed to be significantly slowed down in the presence of MWNTs and an Arrhenius-type behavior, weakly dependent on temperature, is observed at higher frequencies. This non-equilibrium dynamics of PVME is presumed to be originating from interphase regions near the surface of MWNTs. The length scale of the cooperative rearranging region (xi CRR) at T-g, assessed by calorimetric measurements, was observed to be higher in the case of blends with MWNTs. An enhanced molecular level miscibility driven by MWNTs in the blends corroborates with the larger xi CRR and comparatively more number of segments in CRR (in contrast to neat blends) around T-g. The configurational entropy and length scale of the cooperative volume was mapped as a function of temperature in the temperature regime, Tg < T < T-g + 60 K. The blends phase separated by spinodal decomposition which further led to an interconnected PVME network in PS. This further led to materials with very high electrical conductivity upon demixing.

Confinement enhances dispersion in nanoparticle-polymer blend films

Polymer nanocomposites constitute an important class of materials whose properties depend on the state of dispersion of the nanoparticles in the polymer matrix. Here we report the first observations of confinement-induced enhancement of dispersion in nanoparticle-polymer blend films. Systematic variation in the dispersion of nanoparticles with confinement for various compositions and matrix polymer chain dimensions has been observed. For fixed composition, strong reduction in glass transition temperature, T-g, is observed with decreasing blend-film thickness. The enhanced dispersion occurs without altering the polymer-particle interactions and seems to be driven by enhanced matrix-chain orientation propensity and a tendency to minimize the density gradients within the matrix. This implies the existence of two different mechanisms in polymer nanocomposites, which determines their state of dispersion and glass transition.

Local structural distortions and their role in superconductivity in SmFeAsO1-xFx superconductors

EXAFS studies at the As K edge as a function of temperature were carried out in SmFeAsO1-xFx (x = 0 and 0.2) compounds to understand the role of local structural distortions in superconductivity observed in F-doped compounds. A significant correlation between the thermal variation of local structural parameters such as anion height and superconducting onset is found in the fluorinated compounds. Such a variation in anion height is absent in the non-superconducting compound. An increase in the Fe-As bond distance just below the superconducting onset temperature indicates a similarity between the distortions observed in the high-T-C cuprates and these Fe-based superconductors.