Pd and Pt ions as highly active sites for the water-gas shift reaction over combustion synthesized zirconia and zirconia-modified ceria

Noble metal substituted ionic catalysts were synthesized by solution combustion technique. The compounds were characterized by X-ray diffraction, FT-Raman spectroscopy, and X-ray photoelectron spectroscopy. Zirconia supported compounds crystallized in tetragonal phase. The solid solutions of ceria with zirconia crystallized in fluorite structure. The noble metals were substituted in ionic form.The water-gas shift reaction was carried out over the catalysts.Negligible conversions were observed with unsubstituted compounds. The substitution of a noble metal ion was found to enhance the reaction rate. Equilibrium conversion was obtained below 250 degrees C in the presence of Pt ion substituted compounds. The formation of Bronsted acid-Bronsted base pairs was proposed to explain the activity of zirconia catalysts. The effect of oxide ion vacancies on the reactions over substituted ceria-zirconia solid solutions was established. (c)2010 Elsevier B.V. All rights reserved.

Free energy of mixing of divalent basic oxides with silica

An expression derived for the free energy of mixing of a divalent basic oxide (MO) with SiO2 based on a model of silicate structure, takes into account the distribution of O2- (from MO) into the silica network, the mixing of silicate ions with O2- and the enthalpy of mixing. The resulting expression is ΔGmix=RT{N11n (2N1-N)2/4N1(1-N)+N21n N 2-N/1-N}, where N={(β+N1)-√(β+N 1)2-8βN1N2}/2β β=characteristic constant for the system N1=mol fraction of silica N2=mol fraction of MO. For the proper choice of β, calculated values of the activity of MO for the system PbO-SiO2, MnO-SiO2, FeO-SiO2 and CaO-SiO2 are in good agreement with experiment. The model predicts that the activity of the basic oxide decreases with increase in temperature.

Low-temperature polymer precursor-based synthesis of nanocrystalline particles of lanthanum calcium manganese oxide (La0.67Ca0.33MnO3) with enhanced ferromagnetic transition temperature

We report a simple modified polymeric precursor route for the synthesis of highly crystalline and homogenous nanoparticles of lanthanum calcium manganese oxide (LCMO). The LCMO phase formation was studied by thermal analysis, x-ray powder diffraction, and infrared spectroscopy at different stages of heating. These nanocrystallites (average particle size of 30 nm) possess ferromagnetic-paramagnetic transition temperature (T-c) of 300 K, nearly 50 K higher than that of a single crystal. The Rietveld analysis of the powder x-ray diffraction data of the nanopowders reveals significant lattice contraction and reduction in unit cell anisotropy-these structural changes are correlated to the enhancement in T-c.

Spectral studies on pyridinium hexafluorotitanate(IV)

Pure samples of pyridinium hexafluorotitanate(IV) [(C5H5N+H)2TiF=6] were prepared by the reaction of pyridinium poly(hydrogen fluoride) and titanium tetrachloride. The i.r. spectral data in the range 4000–200 cm−1 and 1H, 19F, and 13CNMR spectra for this compound are reported.

Microwave Assisted Synthesis of Nanostructured Titanium Dioxide with High Photocatalytic Activity

TiO2 (anatase) was synthesized using a microwave-irradiation-assisted chemical method. The reaction conditions were varied to obtain unique nanostructures of TiO2 comprising nanometric spheres giving the materials a very porous morphology. The oxide was characterized by X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetric analysis (TGA). The specific surface area and porosity were quantified by the BET method, and the degradation of dyes was carried out using these materials. The photocatalytic activity of the nanometric TiO2 was significantly higher than that of commercially available TiO2 (Degussa P25) for the degradation of the dyes.

Studies in biogas technology. Part IV. A novel biogas plant incorporating a solar water-heater and solar still

A reduction in the heat losses from the top of the gas holder of a biogas plant has been achieved by the simple device of a transparent cover. The heat losses thus prevented have been deployed to heat a water pond formed on the roof of the gas holder. This solar-heated water is mixed with the organic input for ‘ hot-charging ’ of the biogas plant. A thermal analysis of such a solar water-heater ‘ piggy-backing ’ on the gas holder of a biogas plant has been carried out.To test whether the advantages indicated by the thermal analysis can be realised in practice, a biogas plant of the ASTRA design was modified to incorporate a roof-top solar water-heater. The operation of such a modified plant, even under ‘ worst case ’ onditions, shows a significant improvement in the gas yield compared to the unmodified plant. Hence, the innovation reported here may lead to drastic reductions in the sizes and therefore costs of biogas plants. By making the transparent cover assume a tent-shape, the roof-top solar heater can serve the additional function of a solar still to yield distilled water. The biogas plant-cum-solar water-heater-cum-solar still described here is an example of a spatially integrated hybrid device which is extremely cost-effective.

Microstructural changes induced by ternary additions in a hypo-eutectic titanium-silicon alloy

Hypo-eutectic Ti-6.5 wt % Si alloy modified by separate additions of misch metal and low surface tension elements (Na, Sr, Se and Bi) has been examined by microscopic study and thermal analysis. Addition of third element led to modification of microstructure with apparently no significant enhancement of tensile ductility, with the exception of bismuth. Bismuth enhanced the ductility of the alloy by a factor of two and elastic-plastic fracture toughness to 9 MPa m–1/2 from a value of almost zero. The improved ductility of bismuth modified alloy is attributed to the reduced interconnectivity of the eutectic suicide, absence of significant suicide precipitation in the eutectic region and increase in the volume fraction of uniformly distributed dendrites. These changes are accompanied by a decrease in the temperature of eutectic solidification.

On characterization of deformation microstructure in Boron modified Ti-6Al-4V alloy

Addition of boron in small quantities to various titanium alloys have shown significant improvement in mechanical behavior of materials. In the present study, electron back-scatter diffraction (EBSD) techniques have been applied to investigate the deformation microstructure evolution in boron modified two-phase titanium alloy Ti-6Al-4V. The alloy was hot compressed at 750 degrees C up to 50% height reduction at two different strain rates (10(-3) s(-1) and 1 s(-1)). The EBSD analyses indicated significant differences in deformed microstructure of the base alloy and the alloy containing boron. A strong subgrain formation tendency was observed along with inhomogeneous distribution of dislocations inside large a colonies of Ti64. In contrast, a colonies were relatively strain free for Ti64 + B, with more uniform dislocation density distribution. The observed difference is attributed to microstructural modifications viz, grain size refinement and presence of TiB particles at grain boundary produced due to boron addition. (C) 2010 Elsevier B.V. All rights reserved.

Direct Growth of Gold Nanorods on Gold and Indium Tin Oxide Surfaces: Spectral, Electrochemical, and Electrocatalytic Studies

The surfactant-assisted seed-mediated growth method was used for the formation of gold nanorods (GNRs) directly on gold (Au) and indium tin oxide (ITO) surfaces. Citrate-stabilized similar to 2.6 nm spherical gold nanoparticles (AuNPs) were first self-assembled on ITO or Au surfaces modified with (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film and then immersed in a cationic surfactant growth solution to form GNRs. The growth of GNRs on the MPTS sol gel film modified ITO surface was monitored by UV-visible spectroscopy. The ITO surface with the attached spherical AuNPs shows a surface plasmon resonance band at 550 nm. The intensity of this absorption band increases while increasing the immersion time of the AuNP-modified ITO surface into the growth solution, and after 5 h, an additional shoulder band around 680 nm was observed. The intensity of this shoulder band increases, and it was shifted to longer wavelength as the immersion time of the AuNP-modified ITO surface into the growth solution increases. After 20 h, a predominant wave at 720 nm was observed along with a band at 550 nm. Further immersion of the modified ITO surface into the growth solution did not change the absorption characteristics. The bands observed at 550 and 720 nm were characteristics of GNRs, corresponding to transverse and longitudinal waves, respectively. The AFM images showed the presence of GNRs on the surface of the MPTS sol gel modified ITO surface with a typical length of similar to 100-120 nm and a width of similar to 20-22 nm in addition to a few spherical AuNPs, indicating that seeded spherical AuNPs were not completely involved in the GNRs' formation. Finally, the electrocatalytic activity of the surface-grown GNRs on the MPTS sol gel film modified Au electrode toward the oxidation of ascorbic acid (AA) was studied. Unlike a polycrystalline Au electrode, the surface-grown GNR-modified electrode shows two well-defined voltammetric peaks for AA at 0.01 and 0.35 V in alkaline, neutral, and acidic pHs. The cause for the observed two oxidation peaks for AA was due to the presence of both nanorods and spherical nanoparticles on the electrode surface. The presence of spherical AuNPs on the MPTS sol gel film oxidized AA at more positive potential, whereas the GNRs oxidized AA at less positive potential. The observed 340 mV less positive potential shift in the oxidation of AA suggested that GNRs are better electrocatalysts for the oxidation of AA than the spherical AuNPs.

On the evaluation of stability of rare earth oxides as face coats for investment casting of titanium

Attempts have been made to evaluate the thermal stability of rare earth oxide face coats against liquid titanium. Determination of microhardness profiles and concentration profiles of oxygen and metallic constituents of oxide in investment cast titanium rods has allowed grActation of relative stability of rare earth oxides. The relative stability of evaluated oxides in the order of increasing stability follows the sequence CeO2 — ZrO2 — Gd2O3 — didymium oxide — Sm2O3 —Nd2O3 — Y2O3. The grading does not follow the free energy data of the formation of these oxides. A better correlation with the experimental observations is obtained when the solubility of the metallic species in titanium is also taken into consideration.

Synthesis of Novel Oxide Pyrochlores, A2BB?O7 (A = La, Nd; BB? = Pb, Sn, Bi), by Alkali Melt Route

Oxide pyrochlores of the formula A2BB? O7 (A = La, Nd; BB? = Pb, Sn, Bi) have been synthesized by a low-temperature ambient-pressure route employing KOH melts. All the compositions, including La2Bi2O7 and its strontium-substituted derivatives, La2-xSrxBi2O7-?, are deeply colored insulators, confirming that a metallic ground state is not achieved for Pb(IV) and Bi(IV/V) oxides with the pyrochlore structure.

X-ray diffraction line profile analysis of deformation microstructure in boron modified Ti-6Al-4V alloy

X-ray diffraction line profile analysis (XRDLPA) techniques have been applied to investigate the deformed microstructure of a recently developed boron modified two-phase titanium alloy Ti-6Al-4V. The alloy was hot compressed at 750 degrees C up to 50% height reduction at two different strain rates (10(-3) S-1 and 1 S-1). Microstructural parameters like average domain size, average microstrain within the domain and dislocation density of the two phases were determined using X-ray diffraction line profile analysis. The results indicate an increase in the microstrain and dislocation density for the alpha-phase and decrease for the beta-phase in the case of boron modified alloys as compared to the normal material. Microstructural modifications viz, the grain refinement and the presence of hard, brittle TiB particles in the case of boron modified alloy are held responsible for the observed difference in the dislocation density. (C) 2010 Elsevier Inc. All rights reserved.

A modified sulphide capacity function

The sulphide capacity as originally defined by Fincham and Richardson is a strong function of composition in pseudobinary oxide melts of interest in extractive metallurgy. From an analysis of data available in the literature, it is shown that sulphide capacity is directly proportional to the activity of the basic oxide in the melt, within the uncertainty of experimental data. A single parameter is sufficient to describe the sulphide capacity of a binary slag system under isothermal and isobaric conditions. The correlation indicates that the activity coefficient of the sulphide ion or the neutral base metal sulphide dissolved in the melt is independent of composition in pseudobinary melts within experimental uncertainty. Structural variations in the melt with composition do not seem to affect the activity coefficient of the sulphide. A modified sulphide capacity function is defined which makes the treatment more elegant and greatly simplifies data storage and retrieval. The modified function is not based on any model for the melt.

Texture Evolution in Boron Modified Ti-6Al-4V Alloy

Owing to their high strength-to-weight ratio, excellent mechanical properties and corrosion resistance, titanium (Ti) and its alloys, especially (alpha+beta) alloys like Ti-6Al-4V is the backbone materials for aerospace, energy, and chemical industries. Trace boron addition (similar to 0.1 wt. %) to the alloy Ti-6Al-4V produces a reduction in as-cast grain size by roughly an order of magnitude resulting in enhanced ductility, higher stiffness, strength and good fracture resistance. Boron addition could also affect the evolution of texture and microstructure in the material. The solidification microstructures of Boron free as well as Boron containing Ti-6Al-4V are found to be almost homogeneous from periphery towards the center of as-cast ingot in terms of both alpha-colony size and distribution. Boron addition substantially reduces alpha-colony size (similar to 50-80 mu m). A gradual change in alpha texture from periphery towards the center has been observed with orientations close to specific texture components suggesting the formation of texture zones. The mechanism of texture evolution can be visualized as a result of variant selection during solidification through (alpha+beta) phase field.

Rearrangements in the cerium(IV) and manganese(III) oxidations of substituted naphthalenes and the nih shift mechanism

Ceric ammonium sulphate oxidation of 1- and 1,4- disubstituted naphthalenes gives 2- and/or 2,3- disubstituted 1,4- naphthoquinones through migration of substituents (D, Br, Ph). Similar rearrangements are also observed in the manganese(III) oxidation and also in the anodic oxidation of these substrates. The results are consistent with the proposal that these oxidations go through the formation of radical cation followed by reaction with H2O and further oxidation of the radical to the carbocationic intermediate on the way to the corresponding 1,4-naphthoquinone. Oxidation of 1,4-diphenylnaphthalene gives 2,3-diphenyl-1,4-naphthoquinone or 4-hydroxy- 2,4- diphenyl - 1(4)R - naphthalenone. The results are in accordance with the conclusion that such rearrangements do not require prior formation of arene oxide intermediates, originally proposed for the NM shift mechanism.