The glass transition and crystallization kinetic studies on BaNaB9O15 glasses

Transparent glasses of BaNaB9O15 (BNBO) were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were, respectively, confirmed by x-ray powder diffraction and differential scanning calorimetry (DSC). The glass transition and crystallization parameters were evaluated under non-isothermal conditions using DSC. The correlation between the heating rate dependent glass transition and the crystallization temperatures was studied and the Kauzmann temperature was deduced for BNBO glass plates and powdered samples. The values of the Kauzmann temperature for the plates and powdered samples were 776 K and 768 K, respectively. An approximation- free method was used to evaluate the crystallization kinetic parameters for the BNBO glass samples. The effect of the sample thickness on the crystallization kinetics of BNBO glasses was also investigated.

Structural transformations in Mn2NiGa due to residual stress

Powder x-ray diffraction study of Mn2NiGa ferromagnetic shape memory alloy shows the existence of a 7M monoclinic modulated structure at room temperature (RT). The structure of Mn2NiGa is found to be highly dependent on residual stress. For higher stress, the structure is tetragonal at RT, and for intermediate stress it is 7M monoclinic. However, only when the stress is considerably relaxed, the structure is cubic, as is expected at RT since the martensitic transition temperature is 230 K.

Evolution of nanocrystalline BaBi2Nb2O9 in Li2B4O7 BaO-Bi(2)O3-Nb2O5 glass system

Transparent glasses and glass nano crystal composites (GNCs) of various compositions in the system (100 - x)Li2B4O7-x (BaO-Bi2O3-Nb2O5) (where x = 10, 20, and 30 in molar ratio) were fabricated via splat-quenching technique. The glassy nature of the as quenched samples was established by differential thermal analyses. X-ray powder diffraction and transmission electron microscopic (TEM) studies confirmed the formation of layered perovskite BBN via a fluorite like phase. TEM studies revealed the presence of 10 nm sized spherical crystallites of fluorite like BaBi2Nb2O9 phase in the glassy matrix of Li2B4O7 (LBO). The influence of composition on the dielectric and the optical properties (transmission, optical band gap) of these samples has been investigated. (c) 2007 Elsevier B.V. All rights reserved.

Hydrocarbon oxidation and three-way catalytic activity on a single step directly coated cordierite monolith: High catalytic activity of Ce0.98Pd0.02O2−δ

Catalytic activity of cordierite honeycomb by a completely new coating method for the oxidation of major hydrocarbons in exhaust gas is reported here. The new coating process consists of (a) dipping and growing γ-Al2O3 on cordierite by combustion of monolith dipped in the aqueous solution of Al(NO3)3 and oxalyldihydrazide (ODH) (or glycine) at 600 °C and active catalyst phase Ce0.98Pd0.02O2−δ on γ-Al2O3-coated cordierite again by combustion of monolith dipped in the aqueous solution of ceric ammonium nitrate, ODH and 1.2 × 10−3 M PdCl2 solution at 500 °C. Weight of active catalyst can be varied from 0.02 wt% to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion. Adhesion of catalyst to cordierite surface is via oxide growth, which is very strong. ‘HC’ oxidation over the monolith catalyst is carried out with a mixture having the composition, 470 ppm of both propene and propane and 870 ppm of both ethylene and acetylene with the varying amount of O2. Three-way catalytic test is done by putting hydrocarbon mixture along with CO (10 000 ppm), NO (2000 ppm) and O2 (15 000 ppm). Below 350 °C full conversion is achieved. In this method, handling of nano-material powder is avoided.

Synthesis of BaSO4 nanoparticles by precipitation method using sodium hexa metaphosphate as a stabilizer

We describe the synthesis and structure of Barium sulfate nanoparticles by precipitation method in the presence of water soluble inorganic stabilizing agent, sodium hexametaphosphate, (NaPO3)(6). The structural parameters were refined by the Rietveld refinement method using powder X-ray diffraction data. Barium sulfate nanoparticles were crystallized in the orthorhombic structure with space group Pbnm (No. 62) having the lattice parameters a = 7.215(1) (angstrom), b = 8.949(1) (angstrom) and c = 5.501 (1) (angstrom) respectively. Transmission electron microscopy study reveals that the nanoparticles are size range, 30-50 nm. Fourier transform infrared spectra showed distinct absorption due to the SO42- moiety at 1115 and 1084 cm(-1) indicating formation of barium sulfate nanoparticles free from the phosphate group from the stabilizer used in the synthesis. (C) 2009 Elsevier Ltd. All rights reserved.

Soy supplementation and role of equol production capability in postmenopausal women using tibolone: effects on cardiovascular risk markers

Tibolone, a synthetic steroid, is effective in the treatment of postmenopausal symptoms. Its cardiovascular safety profile has been questioned, because tibolone reduces the levels of high-density lipoprotein (HDL) cholesterol. Soy-derived isoflavones may offer health benefits, particularly as regards lipids and also other cardiovascular disease (CVD) risk factors. The soy-isoflavone metabolite equol is thought to be the key as regards soy-related beneficial effects. We studied the effects of soy supplementation on various CVD risk factors in postmenopausal monkeys and postmenopausal women using tibolone. In addition, the impact of equol production capability was studied. A total of 18 monkeys received casein/lactalbumin (C/L) (placebo), tibolone, soy (a woman s equivalent dose of 138 mg of isoflavones), or soy with tibolone in a randomized order for 14 weeks periods, and there was a 4-week washout (C/L) in between treatments. Postmenopausal women using tibolone (N=110) were screened by means of a one-week soy challenge to find 20 women with equol production capability (4-fold elevation from baseline equol level) and 20 control women, and treated in a randomized cross-over trial with a soy powder (52 g of soy protein containing 112 mg of isoflavones) or placebo for 8 weeks. Before and after the treatments lipids and lipoproteins were assessed in both monkeys and women. In addition, blood pressure, arterial stiffness, endothelial function, sex steroids, sex hormone-binding globulin (SHBG), and vascular inflammation markers were assessed. A 14% increase in plasma low-density lipoprotein (LDL) + very low-density lipoprotein (VLDL) cholesterol was observed in tibolone-treated monkeys vs. placebo. Soy treatment resulted in a 18% decrease in LDL+VLDL cholesterol, and concomitant supplementation with tibolone did not negate the LDL+VLDL cholesterol-lowering effect of soy. A 30% increase in HDL cholesterol was observed in monkeys fed with soy, whereas HDL cholesterol levels were reduced (48%) after tibolone. Interestingly, Soy+Tibolone diet conserved HDL cholesterol levels. Tibolone alone increased the total cholesterol (TC):HDL cholesterol ratio, whereas it was reduced by Soy or Soy+Tibolone. In postmenopausal women using tibolone, reductions in the levels of total cholesterol and LDL cholesterol were seen after soy supplementation compared with placebo, but there was no effect on HDL cholesterol, blood pressure, arterial stiffness or endothelial function. Soy supplementation decreased the levels of estrone in equol producers, and those of testosterone in the entire study population. No changes were seen in the levels of androstenedione, dehydroepiandrosterone sulfate, or SHBG. The levels of vascular cell adhesion molecule-1 increased, and platelet-selectin decreased after soy treatment, whereas C-reactive protein and intercellular adhesion molecule-1 remained unchanged. At baseline and unrelated to soy treatment, equol producers had lower systolic, diastolic and mean arterial pressures, less arterial stiffness and better endothelial function than non-producers. To conclude, soy supplementation reversed the tibolone-induced fall in HDL cholesterol in postmenopausal monkeys, but this effect was not seen in women taking tibolone. Equol production capability was associated with beneficial cardiovascular changes and thus, this characteristic may offer cardiovascular benefits, at least in women using tibolone.

PVA-PSSA Membrane with Interpenetrating Networks and its Methanol Crossover Mitigating Effect in DMFCs

A membrane with interpenetrating networks between poly(vinyl alcohol) (PVA) and poly(styrene sulfonic acid) (PSSA) coupled with a high proton conductivity is realized and evaluated as a proton exchange membrane electrolyte for a direct methanol fuel cell (DMFC). Its reduced methanol permeability and improved performance in DMFCs suggest the new blend as an alternative membrane to Nafion membranes. The membrane has been characterized by powder X-ray diffraction, scanning electron microscopy, time-modulated differential scanning calorimetry, and thermogravimetric analysis in conjunction with its mechanical strength. The maximum proton conductivity of 3.3×10−2 S/cm for the PVA–PSSA blend membrane is observed at 373 K. From nuclear magnetic resonance imaging and volume localized spectroscopy experiments, the PVA–PSSA membrane has been found to exhibit a promising methanol impermeability, in DMFCs. On evaluating its utility in a DMFC, it has been found that a peak power density of 90 mW/cm2 at a load current density of 320 mA/cm2 is achieved with the PVA–PSSA membrane compared to a peak power density of 75 mW/cm2 at a load current density of 250 mA/cm2 achievable for a DMFC employing Nafion membrane electrolyte while operating under identical conditions; this is attributed primarily to the methanol crossover mitigating property of the PVA–PSSA membrane.

Surfactant stabilized nanopetals morphology of α-MnO2 prepared by microemulsion method

α-Manganese dioxide is synthesized in a microemulsion medium by a redox reaction between KMnO4 and MnSO4 in presence of sodium dodecyl sulphate as a surface active agent. The morphology of MnO2 resembles nanopetals, which are spread parallel to the field. The material is further characterized by powder X-ray diffraction, energy dispersive analysis of X-ray, and Brunauer–Emmett–Teller surface area. Supercapacitance property of α-MnO2 nanopetals is studied by cyclic voltammetry and galvanostatic charge–discharge cycling. High values of specific capacitance are obtained.

Synthesis and characterization of nano-MnO2 for electrochemical supercapacitor studies

Nanostructured MnO2 was synthesized at ambient condition by reduction of potassium permanganate with aniline. Powder X-ray diffraction, thermal analysis (thermogravimetric and differential thermal analysis), Brunauer-Emmett-Teller surface area, and infrared spectroscopy studies were carried out for physical and chemical characterization. The as-prepared MnO2 was amorphous and contained particles of 5-10 nm diameter. Upon annealing at temperatures >400°C, the amorphous MnO2 attained crystalline α-phase with a concomitant change in morphology. A gradual conversion of nanoparticles to nanorods is evident from scanning electron microscopy and transmission electron microscopy (TEM) studies. High-resolution TEM images suggested that nanoparticles and nanorods grow in different crystallographic planes. Capacitance behavior was studied by cyclic voltammetry and galvanostatic charge-discharge cycling in a potential range from -0.2 to 1.0 V vs SCE in 0.1 M sodium sulfate solution. Specific capacitance of about 250 F g-1 was obtained at a current density of 0.5 mA cm-2(0.8 A g-1).

Synthesis of Cu@ZnO Core−Shell Nanocomposite through Digestive Ripening of Cu and Zn Nanoparticles

The synthesis of colloids of copper and zinc nanoparticles by solvated metal atom dispersion (SMAD) is described. The as-prepared colloids with a large size distribution of the particles are transformed into colloidal nanoparticles of a narrow size distribution by the digestive ripening process which involves refluxing the colloid at or near the boiling point of the solvent in the presence of a passivating ligand. The copper nanoparticles of 2.1 ± 0.3 nm and zinc nanoparticles of 3.9 ± 0.3 nm diameters have thus been obtained. Digestive ripening of the as-prepared copper and zinc colloids together in the presence of a passivating agent gave Cu@ZnO core−shell nanoparticles, with an average diameter of 3.0 ± 0.7 nm. Particles synthesized in this manner were characterized by UV−visible spectroscopy, high-resolution electron microscopy, energy-filtered electron microscopy, and powder X-ray diffraction methods which confirm the core−shell structure.

Size-dependent magnetic properties of iron carbide nanoparticles embedded in a carbon matrix

Here we report on the magnetic properties of iron carbide nanoparticles embedded in a carbon matrix. Granular distributions of nanoparticles in an inert matrix, of potential use in various applications, were prepared by pyrolysis of organic precursors using the thermally assisted chemical vapour deposition method. By varying the precursor concentration and preparation temperature, compositions with varying iron concentration and nanoparticle sizes were made. Powder x-ray diffraction, transmission electron microscopy and Mossbauer spectroscopy studies revealed the nanocrystalline iron carbide (Fe3C) presence in the partially graphitized matrix. The dependence of the magnetic properties on the particle size and temperature (10 K < T < 300 K) were studied using superconducting quantum interference device magnetometry. Based on the affect of surrounding carbon spins, the observed magnetic behaviour of the nanoparticle compositions, such as the temperature dependence of magnetization and coercivity, can be explained.

Hydrothermal synthesis and characterization of CaSO4 pseudomicrorods

Calcium sulphate (CaSO4) pseudomicrorods have been synthesized by alow-temperature hydrothermal method using CaSO4 powder as a precursor and hexadecylamine as a surfactant at 180 degrees C for at different intervals of time. The powder X-ray diffraction pattern indicates that the as-formed pseudomicrorods are of orthorhombic phase with lattice parameters a = 7.0023(4) angstrom, b = 6.9939(5) angstrom and c = 6.2434(4) angstrom. Scanning electron microscopy images show that the pseudomicrorods have diameters of about 0.2-2.5 mm and lengths of about 2-10 mm. Fourier transform infrared spectroscopy shows a strong doublet near 609 and 681 cm(-1) arising from nu(4) (SO42) bending vibrations. The strongest band observed at 1132 cm(-1) is associated with nu(3) (SO42-) stretching vibrations. The band near 420-450 cm(-1) is attributed to nu(2) (SO42-) bending vibrations. The Raman spectrum exhibits an intense peak at 1008 cm(-1) associated with the SO42- mode. The photoluminescence spectrum exhibits UV bands (330, 350 nm), strong green bands (402, 436 nm) and weak blue bands (503 nm). A widening of the optical band gap was observed as the particle size decreased.

Unraveling the packing pattern leading to gelation using SS NMR and X-ray diffraction: direct observation of the evolution of self-assembled fibers

A detailed understanding of the mode of packing patterns that leads to the gelation of low molecular mass gelators derived from bile acid esters was carried out using solid state NMR along with complementary techniques such as powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and polarizing optical microscopy (POM). Solid state C-13{H-1} cross polarization (CP) magic angle spinning (MAS) NMR of the low molecularmass gel in its native state was recorded for the first time. A close resemblance in the packing patterns of the gel, xerogel and bulk solid states was revealed upon comparing their C-13{H-1} CPMAS NMR spectral pattern. A doublet resonance pattern of C-13 signals in C-13{H-1}CPMAS NMR spectra were observed for the gelator molecules, whereas the non-gelators showed simple singlet resonance or resulted inthe formation of inclusion complexes/solvates. PXRD patterns revealed a close isomorphous nature of the gelators indicating the similarity in the mode of the packing pattern in their solid state. Direct imaging of the evolution of nanofibers (sol-gel transition) was carried out using POM, which proved the presence of self-assembled fibrillar networks (SAFINs) in the gel. Finally powder X-ray structure determination revealed the presence of two non-equivalent molecules in an asymmetric unit which is responsible for the doublet resonance pattern in the solid state NMR spectra.

Study on Young's modulus and microhardness of carbon nanotubes reinforced copper nanocomposite

Carbon nanotubes (CNTs) were discovered by Iijima in 1991 as the fourth form of carbon. Carbon nanotubes are the ultimate form of the carbon fibre because of its high Young's modulus in the order of 1 TPa, which is very useful for load transfer in nanocomposites. In the present work, CNT/Cu nanocomposites were fabricated by the powder metallurgy technique, and after extrusion of the nanocomposites, bright field transmission electron microscopic studies were carried out. From the transmission electron microscopic images obtained, a novel method of ascertaining the Young's modulus of multiwalled CNTs is worked out in the present paper, which turns out to be 0.94 TPa, which is consistent with experimental results. Furthermore, an attempt is made to investigate the microhardness of copper by reinforcing it with multiwalled CNTs. There is an increase in hardness by twofold in CNT/Cu nanocomposites as compared to pure Cu matrix. This is due to high relative density, even distribution of CNTs and proper bonding at CNT/Cu interfaces.

NMR study of internal motions in certain iron group fluosilicates

NMR study of ferrous fluosilicate hexahydrate indicated the presence of motion of both proton and fluorine nuclei. Only a single narrow line was observed for protons for any arbitrary orientation of a single crystal with respect to the applied magnetic field. This can be interpreted in terms of a phase-correlated flip motion of the interproton vectors between two disordered orientations or in terms of a hindered rotation of the Fe(H2O) 6 octahedron about the fourfold axes, together with the flip motion. The fluorine second moment indicated that the SiF6 octahedron also is undergoing reorientation. The temperature variation of the powder linewidth showed a transition around 195°K and led to rather low values for the potential barriers hindering the motions. No significant temperature variation of the linewidth was observed for hexahydrated cobalt fluosilicate in the temperature range between 90°K and room temperature. Similar observations in a powder sample of tetrahydrated copper fluosilicate also showed the presence of internal motions. The linewidth transition in this case took place at about 220°K and was found to be rather abrupt. The potential barrier for the motion was found to be relatively high.