System Nd-Pd-O: Phase diagram and thermodynamic properties of oxides using a solid-state cell with advanced features

An isothermal section of the phase diagram for the system Nd-Pd-O at 1350 K has been established by equilibration of samples representing 13 different compositions and phase identification after quenching by optical and scanning electron microscopy, x-ray diffraction, and energy dispersive analysis of x-rays. The binary oxides PdO and NdO were not stable at 1350 K. Two ternary oxides Nd4PdO7 and Nd2Pd2O5 were identified. Solid and liquid alloys, as well as the intermetallics NdPd3 and NdPd5, were found to be in equilibrium with Nd2O3. Based on the phase relations, three solidstate cells were designed to measure the Gibbs energies of formation of PdO and the two ternary oxides. An advanced version of the solid-state cell incorporating a buffer electrode was used for high-temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MP a as the reference electrode. Electromotive force measurements, conducted from 950 to 1425 K, indicated the presence of a third ternary oxide Nd2PdO4, stable below 1135 (±10) K. Additional cells were designed to study this compound. The standard Gibbs energy of formation of PdO (†f G 0) was measured from 775 to 1125 Kusing two separate cell designs against the primary reference standard for oxygen chemical potential. Based on the thermodynamic information, chemical potential diagrams for the system Nd-Pd-O were also developed.

Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO(2) thin films by DC magnetron sputtering

Titanium dioxide (TiO(2)) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO(2) films has been analyzed by X-ray photoelectron spectroscopy. The TiO(2) films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO(2) into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO(2)/p-Si have been fabricated. The leakage current density of unbiased films was 1 x10(-6) A/cm(2) at a gate bias voltage of 1.5 V and it was decreased to 1.41 x 10(-7) A/cm(2) with the increase of substrate bias voltage to -150 V owing to the increase in thickness of interfacial layer of SiO(2). Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at -150 V. The capacitance at 1 MHz for unbiased films was 2.42 x 10(-10) F and it increased to 5.8 x 10(-10) F in the films formed at substrate bias voltage of -150 V. Dielectric constant of TiO(2) films were calculated from capacitance-voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at -150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to -150 V. (C) 2011 Elsevier B. V. All rights reserved.

An eight-connected metal organic framework based on Cu(5) clusters: Synthesis, structure, magnetic and catalytic properties

A reaction of copper acetate, 5-nitroisophthalic acid in a water-methanol mixture under solvothermal condition results in a new metal-organic framework compound, [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, (1). The compound contains Cu5 pentameric cluster units connected by 5-nitro isophthalate (NIPA) moieties forming a CdCl(2)-like layer, which are further connected by another NIPA moiety forming the three-dimensional structure. The water molecules in (1) can be reversibly adsorbed. The removal of water accompanies a change in the colour as well as a structural re-organization. Magnetic studies suggest strong antiferromagnetie correlations between the Cu5 cluster units. The compound (1) exhibits heterogeneous Lewis acid catalysis for the cyanosilylation of imines with more than 95 % selectivity. Compound (1) has been characterized by IR, UV-vis, TGA, powder XRD studies.

Growth, magnetotransport, and magnetic properties of ferromagnetic (In,Mn)Sb crystals

In1−xMnxSb crystals are grown with different Mn doping concentrations (x = 0.006, 0.01, 0.02, and 0.04) beyond the equilibrium solubility limit by the horizontal Bridgman technique. Structural, magnetic, and magnetotransport properties of the grown crystals are studied in the temperature range 1.4–300 K. Negative magnetoresistance and anomalous Hall effect are observed below 10 K. The anomalous Hall coefficient is found to be negative. The temperature dependence of the magnetization measurement shows a magnetic ordering below 10 K, which could arise from InMnSb alloy formation. Also, the saturation in magnetization observed even at room temperature suggests the existence of ferromagnetic MnSb clusters in the crystals, which has been verified by scanning electron microscopy studies. The carrier concentration increases with Mn doping, and this results in a decrease of resistivity. The carrier concentration and mobility at room temperature for the doped crystals are ∼ 2×1019 cm−3 and ∼ 200 cm2/V s, respectively. The observed anomalous Hall effect suggests the carrier mediated ferromagnetism below 10 K in In1−xMnxSb crystals.

Growth and ferroelectric properties of Bi2VO5.5 thin films with metallic LaNiO3 electrodes

Novel ferroelectric bismuth vanadate, Bi2VO5.5 (BVO), thin films have been grown between lattice matched metallic LaNiO3 (LNO) layers deposited on SrTiO3 (STO) by the pulsed laser deposition technique. LNO/BVO/LNO/STO and Au/BVO/LNO/STO trilayer structures exhibited c‐oriented (001) growth of BVO. LNO has been found to be a good metallic electrode with sheet resistance ∼20 Ω in addition to aiding c‐axis oriented BVO growth. The dielectric constant, ϵr of LNO/BVO/LNO/STO, at 300 K was about 12. However, when an Au electrode was used on top of BVO/LNO/STO film, it showed a significant improvement in the dielectric constant (ϵr=123). The ferroelectric properties of BVO thin films have been confirmed by hysteresis behavior with a remnant polarization, Pr=4.6×10−8 C/cm2 and coercive field, Ec=23 kV/cm at 300 K.

Biological and materials properties of various cholesterol based systems

Liposomes composed of cationic lipids have become very popular gene delivery vehicles. A great deal of research is being pursued to make efficient vectors by varying their molecular architecture. Cholesterol being ubiquitous component in most of the animal cell membranes is increasingly being used as a hydrophobic segment of synthetic cationic lipids. In this review we describe various cholesterol based cationic lipids and focus on the effect of modifying various structural segments like linker and the head group of the cationic lipids on gene transfection efficiency with a special emphasis on the importance of ether linkage between cholesteryl backbone and the polar head group. Interaction of cationic cholesteryl lipids with dipalmitylphosphatidycholine membranes is also discussed here. Apart from cholesterol being an attractive scaffold in the drug/gene delivery vehicles, certain cholesteryl derivatives have also been shown to be attractive room temperature liquid-crystalline materials.

Optical, electrical and structural characterization of ZnO:Al thin films prepared by a low cost sol-gel method

ZnO:Al thin films were prepared on glass and silicon substrates by the sol-gel spin coating method. The x-ray diffraction (XRD) results showed that a polycrystalline phase with a hexagonal structure appeared after annealing at 400 degrees C for 1 h. The transmittance increased from 91 to about 93% from pure ZnO films to ZnO film doped with 1 wt% Al and then decreased for 2 wt% Al. The optical band gap energy increased as the doping concentration was increased from 0.5 wt% to 1 wt% Al. The metal oxide semiconductor (MOS) capacitors were fabricated using ZnO films deposited on silicon (100) substrates and electrical properties such as current versus voltage (I-V) and capacitance versus voltage (C-V) characteristics were studied. The electrical resistivity decreased and the leakage current increased with an increase of annealing temperature. The dielectric constant was found to be 3.12 measured at 1 MHz. The dissipation value for the film annealed at 300 degrees C was found to be 3.1 at 5 V. (C) 2011 Elsevier Ltd. All rights reserved.

Near-Room-Temperature Colossal Magnetodielectricity and Multiglass Properties in Partially Disordered La2NiMnO6

We report magnetic, dielectric, and magnetodielectric responses of the pure monoclinic bulk phase of partially disordered La2NiMnO6, exhibiting a spectrum of unusual properties and establish that this compound is an intrinsically multiglass system with a large magnetodielectric coupling (8%-20%) over a wide range of temperatures (150-300 K). Specifically, our results establish a unique way to obtain colossal magnetodielectricity, independent of any striction effects, by engineering the asymmetric hopping contribution to the dielectric constant via the tuning of the relative-spin orientations between neighboring magnetic ions in a transition-metal oxide system. We discuss the role of antisite (Ni-Mn) disorder in emergence of these unusual properties.

Synthesis, Structure, and Magnetic Properties of a New Eight-Connected Metal-Organic Framework (MOF) based on Co-4 Clusters

A hydrothermal reaction of cobalt nitrate, 4,4'-oxybis(benzoic acid) (OBA), 1,2,4-triazole, and NaOH gave rise to a deep purple colored compound Co-4(triazolate)(2)(OBA)(3)], I, possessing Co-4 clusters. The Co-4 clusters are connected together through the tirazolate moieties forming a two-dimensional layer that closely resembles the TiS2 layer. The layers are pillared by the OBA units forming the three-dimensional structure. To the best of our knowledge, this is the first observation of a pillared TiS2 layer in a metal-organic framework compound. Magnetic studies in the temperature range 1.8-300 K indicate strong antiferromagetic interactions for Co-4 clusters. The structure as well as the magnetic behavior of the present compound has been compared with the previously reported related compound Co-2(mu 3-OH)(mu(2)-H2O)(pyrazine)(OBA)(OBAH)] prepared using pyrazine as the linker between the Co-4 clusters.

Influence of minor addition of boron on tensile and fatigue properties of wrought Ti-6Al-4V alloy

Addition of boron to cast Ti-6Al-4V alloy leads to significant refinement in grain size, which in turn improves processibilty as well as the mechanical properties of the as-cast alloy. Room temperature tensile and fatigue properties of Wrought Ti-6Al-4V-B alloys with B up to 0.09 wt.% are investigated. Thermo-mechanical processing at 950 degrees C caused kinking of alpha lamellae and alignment of TiB particles in the flow direction with a negligible change in prior beta grain and colony sizes, indicating the absence of dynamic recrystallisation during forging. Characterisation with the aid of X-ray and electron back scattered diffraction reveal a strong basal texture in B free alloy which gets randomised with the 0.09B addition in the forged condition. Marginal enhancement in tensile and fatigue properties upon forging is noted. B free wrought Ti-6Al-4V alloy exhibits better tensile strength as compared to B containing alloy, due to the operation of < c+a > slip on pyramidal planes with high value of CRSS as compared to < a > slip on basal and prismatic planes. Decrease in fatigue strength of Ti-6Al-4V-0.04B in as-cast and the wrought state is observed due to increase in the volume fraction of grain boundary a phase with B addition, which acts as a crack nucleation site. No significant effect of TiB particles on tensile and fatigue properties is observed. (C) 2012 Elsevier B.V. All rights reserved.

Characterisation of microstructure and evaluation of optical and EPR properties of superhydrophobic copper dodecanoate films

Copper dodecanoate films prepared by emulsion method exhibit superhydrophobic property with water contact angle of 155 degrees and sliding angle of <2 degrees. The films have been characterised by using X-ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy techniques. Surface microstructure of copper dodecanoate consists of numerous microscale papillas of about 6-12 mu m in length with a diameter in the range of 360-700 nm. The superhydrophobicity of the films is due to their dual micronano surface morphology. The wetting behaviour of the film surface was studied by a simple water immersion test. The results show that copper dodecanoate film retained superhydrophobic property even after immersing in water for about 140 h. The optical absorption spectrum exhibits two broadbands centred at 388 and 630 nm that have been assigned to B-2(1g) -> E-2(g) and B-2(1g) -> B-2(2g) transitions of Cu2+ ions, respectively. The electron paramagnetic resonance spectrum exhibits two resonance signals with effective g values at g(parallel to)approximate to 2.308 and g(perpendicular to) approximate to 2.071, which suggests that the unpaired electron occupies d(x2-y2) orbital in the ground state. Copyright (C) 2011 John Wiley & Sons, Ltd.

Synthesis, characterization, thermo- and photoluminescence properties of Bi3+ co-doped Gd2O3:Eu3+ nanophosphors

Gd2O3:Eu3+ (4 mol%) co-doped with Bi3+ (Bi = 0, 1, 3, 5, 7, 9 and 11 mol%) ions were synthesized by a low-temperature solution combustion method. The powders were calcined at 800A degrees C and were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), Fourier transform infrared and UV-Vis spectroscopy. The PXRD profiles confirm that the calcined products were in monoclinic with little cubic phases. The particle sizes were estimated using Scherrer's method and Williamson-Hall plots and are found to be in the ranges 40-60 nm and 30-80 nm, respectively. The results are in good agreement with TEM results. The photoluminescence spectra of the synthesized phosphors excited with 230 nm show emission peaks at similar to 590, 612 and 625 nm, which are due to the transitions D-5(0)-> F-7(0), D-5(0)-> F-7(2) and D-5(0)-> F-7(3) of Eu3+, respectively. It is observed that a significant quenching of Eu3+ emission was observed under 230 nm excitation when Bi3+ was co-doped. On the other hand, upon 350 nm excitation, the luminescent intensity of Eu3+ ions was enhanced by incorporation of Bi3+ (5 mol%) ions. The introduction of Bi3+ ions broadened the excitation band of Eu3+ of which a new strong band occurred ranging from 320 to 380 nm. This has been attributed to the 6s(2)-> 6s6p transition of Bi3+ ions, implying a very efficient energy transfer from Bi3+ ions to Eu3+ ions. The gamma radiation response of Gd2O3:Eu3+ exhibited a dosimetrically useful glow peak at 380A degrees C. Using thermoluminescence glow peaks, the trap parameters have been evaluated and discussed. The observed emission characteristics and energy transfer indicate that Gd2O3:Eu3+, Bi3+ phosphors have promising applications in solid-state lighting.

Thermo-physical and structural studies of sodium zinc borovanadate glasses in the region of high concentration of modifier oxides

This paper reports investigation of Na2O and ZnO modified borovanadate glasses in the highly modified regime of compositions. These glasses have been prepared by microwave route. Ultraviolet (UV) and visible, infrared (IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies have been used to characterize the speciation in the glasses. Together with the variation of properties such as molar volume and glass transition temperatures, spectroscopic data indicate that at high levels of modification, ZnO tends to behave like network former. It is proposed that the observed variation of all the properties can be reasonably well understood with a structural model. The model considers that the modification and speciation in glasses are strongly determined by the hierarchy of group electronegativities. Further, it is proposed that the width of the transitions of glasses obtained under same condition reflects the fragility of the glasses. An empirical expression has been suggested to quantify fragility on the basis of width of the transition regions. (C) 2012 Elsevier Ltd. All rights reserved.

Asymmetric and symmetric rolling of magnesium: Evolution of microstructure, texture and mechanical properties

In the present study, asymmetric rolling was carried out for incorporating a shear component during the rolling at different temperatures, and was compared with conventional (symmetric) rolling. The microstructures were investigated using electron back-scatter diffraction (EBSD). The strain incorporated was compared with the help of grain orientation spread (GOS). GOS was eventually used as a criterion to partition the microstructure for separating the deformed and the dynamically recrystallized (DRX) grains. The texture of the partitioned DRX grains was shifted by similar to 30 degrees along the c-axis from the deformed grains. The mechanism of dynamic recrystallization (DRX) has been identified as continuous dynamic recovery and recrystallization (CDRR). The partitioned deformed grains for the higher temperature rolled specimens exhibited a texture similar to the room temperature rolled specimen. The asymmetric rolling introduces a shear component which shifts the texture fibre by similar to 5-10 degrees from the conventional rolling texture. This led to an increase in ductility with little compromise on strength. (c) 2012 Elsevier B.V. All rights reserved.

High Temperature Phase Transition Studies and Dielectric Properties of Sr2SbMnO6

Sr2SbMnO6 (SSMO) ceramics were, fabricated using the nanocrystalline powders obtained via molten salt synthesis (MSS) method. High temperature X-ray diffraction studies confirmed the structural phase transition (room temperature tetragonal (I4/mcm) to the cubic phase (Pm-3m)) temperature to be around 736K. The discontinuity in the phase transition indicated its first order nature reflecting the presence of ferroelectric-like distortions in SSMO prepared from MSS which seemed to be unique as it was not observed so far in the case of SSMO prepared using solid-state reaction method. The dielectric behavior of SSMO was studied in the 300-950 K temperature range at high frequencies (MHz range) in order to suppress the of space charge and related effects that dominate at such higher temperatures and mask the real phase transition.