An electron spectroscopic study of the adsorption of nitrogen on a Ni/TiO2 catalyst prepared in situ in the spectrometer: evidence for dissociative adsorption in the strong-metal-support-interaction (SMSI) state

Nitrogen is dissociatively adsorbed on an annealed Ni/TiO2 surface just as on a Ti–Ni alloy surface while it is molecularly adsorbed on a Ni/Al2O3 surface.

Synthesis, infrared spectra and thermoanalytical properties of transition metal sulfite hydrazine hydrates

Transition metal sulfite hydrazine hydrates, MSO3·xN2H4·yH2O whereM=Mn, Fe, Co, Ni and Zn have been prepared and characterized by chemical analysis, infrared spectra, thermoanalytical and combustion studies. The colours,x andy parameters of the complexes varied depending upon the preparation conditions. Thermal decomposition characteristics differ from metal to metal yielding metal oxides at relatively low temperatures.Mittels chemischer Analyse, IR-Spektren, thermoanalytischen und Verbrennungsstudien wurden die Hydrazinhydrate der hergestellten Übergangsmetallsulfite MSO3·xN2H4·yH2O mitM=Mn, Fe, Co, Ni und Zn beschrieben. Farbe sowie die Parameterx undy der Komplexe hängen von den Herstellungsbedingungen ab. Die thermische Zersetzung, bei der bei relativ niedrigen Temperaturen Metalloxide entstehen, ist von Metall zu Metall verschieden.

Singlet quenching of tetraphenylporphyrin and its metal derivatives by iron(III) coordination compounds

The quenching of fluorescence of the free-base tetraphenylporphyrin, H2TPP, and its metal derivatives, MgTPP and ZnTPP by diverse iron(III) complexes, [Fe(CN)6]3−, Fe(acac)3, [Fe(mnt)2]−, Fe(Salen)Cl, [Fe4S4(SPh)4]2−·, FeTPPCl and [Fe(Cp)2]+ has been studied both in homogeneous medium (CH3CN) and micellar media, SDS., CTAB and Triton X-100. The quenching efficiencies are analysed in terms of diffusional encounters and it has been possible to separate static quenching components. The quenching constants are dependent on the nature of the ligating atoms around iron(III) and also on the extent of π-conjugation of the ligands. The quenching mechanism has been investigated using steady-state irradiation experiments. Evidence for oxidative quenching by iron(III) complexes was obtained, though the spin multiplicities of the excited electronic states of iron(III) complexes permit both energy and electron transfer mechanisms for quenching of the singlet excited state of the porphyrins.

A novel metal binding mode of a pyrimidine nucleotide. Crystal structure of [Cu(5′-UMP)(im)2(H2O)]·4H2O

X-ray analysis of the ternary complex [Cu(5′-UMP)(im)2(H2O)]·4H2O, where 5′-UMP uridine-5′-monophosphate and IM = imidazole, reveals a novel metal binding mode of pyrimidine nucleotide through the ribose group.

Combustion Synthesis of Metal Chromite Powders

Fine-particle metal chromites (MCr2O4, where M = Mg, Ca, Mn, Fe, Co, Ni, Cu, and Zn) have been prepared by the combustion of aqueous solutions containing the respective metal nitrate, chromium(III) nitrate, and urea in stoichiometric amounts. The mixtures, when rapidly heated to 350°C, ignite and yield voluminous chromites with surface areas ranging from 5 to 25 m2/g. MgCr2O4, sintered in air at 1500°C for 5 h, has a density of 4.0 g/cm3.

Electrobioleaching of base metal sulfides

Bioleaching of base metal sulfides, such as pyrite, chalcopyrite, and sphalerite, under the influence of applied direct current (DC) potentials is discussed. Contributions toward mineral dissolution from three effects, namely, galvanic, applied potential, and microbiological, are analyzed and compared. Sphalerite could be selectively bioleached in the presence of Thiobacillus ferrooxidans under an applied potential of -500 mV (SCE) from mixed sulfides containing sphalerite, pyrite, and chalcopyrite. Bacterial activity and growth were found to be promoted under electrobioleaching conditions. Probable mechanisms involved in the bioleaching of different sulfides under positive and negative applied potentials are discussed.

Influence of Die Surface Textures during Metal Forming-A Study Using Experiments and Simulation

Friction plays an important role in metal forming processes, and the surface texture of the die is a major factor that influences friction. In the present investigation, experiments were conducted to understand the role of surface texture of the harder die surface and load on coefficient of friction. The data analysis showed that the coefficient of friction is highly dependent on the surface texture of the die surface. Assigning different magnitude of coefficients of friction, obtained in the experiments, at different regions between the die and the workpiece, Finite element (FE) simulation of a compression test was carried out to understand the effect of friction on deformation and stress/strain-rate distribution. Simulation results revealed that, owing to the difference in coefficient of friction, there is a change in metal flow pattern. Both experimental and simulation results confirmed that the surface texture of the die surface and thus coefficient of friction directly affects the strain rate and flow pattern of the workpiece.

Characterization of defects in gallium arsenide

It is well-known that the properties of semiconductor materials including gallium arsenide are controlled by defects and impurities. The characterization of these defects is important not only for better understanding of the solid state phenomena but also for improved reliability and performance of electronic devices. We have been investigating the defects in gallium arsenide for several years using deep level transient spectroscopy, photoconductivity, transient photoconductivity, photoluminescence etc. Results drawn from our recent studies are presented here to illustrate some of the problems concerning transition metal impurities, process-induced defects, occurrence of intracentre transitions and metastability of deep levels in gallium arsenide.

Noble metal ionic sites for catalytic hydrogen combustion: spectroscopic insights

A catalytic hydrogen combustion reaction was carried out over noble metal catalysts substituted in ZrO2 and TiO2 in ionic form. The catalysts were synthesized by the solution combustion technique. The compounds showed high activity and CO tolerance for the reaction. The activity of Pd and Pt ion substituted TiO2 was comparable and was higher than Pd and Pt ion substituted ZrO2. The mechanisms of the reaction over the two supports were proposed by making use of the X-ray photoelectron spectroscopy and FT infrared spectroscopic observations. The reaction over ZrO2 supported catalysts was proposed to take place by the utilization of the surface hydroxyl groups while the reaction over TiO2 supported catalysts was hypothesized to be a hybrid mechanism utilizing surface hydroxyl groups and the lattice oxygen.

A study of chemically prepared small metal clusters in the nonmetallic regime

Small gold clusters [mean diameter (d)[less, similar] 1.4 nm], unlike larger clusters, show a higher Au(4f) binding energy relative to the bulk value and the presence of a conductance gap in tunnelling measurements, just as the molecular cluster compound, Au55(PPh3)12Cl6; small platinum clusters show similar nonmetallic features.

Combustion synthesis and properties of fine-particle rare-earth-metal zirconates, Ln2Zr2O7

Fine-particle rare-earth-metal zirconates, Ln2Zr2O7, where Ln = La, Ce, Pr, Nd, Sm, Gd and Dy having the pyrochlore structure have been prepared using a novel combustion process. The process employs aqueous solutions of the corresponding rare-earth-metal nitrate, zirconium nitrate and carbohydrazide/urea in the required molar ratio. When the solution is rapidly heated to 350–500 °C it boils, foams and burns autocatalytically to yield voluminous oxides. The formation of single-phase Ln2Zr2O7 has been confirmed by powder X-ray diffraction, infrared and fluorescence spectroscopy. The solid combustion products are fine, having surface areas in the range 6–20 m2 g–1. The cold-pressed Pr2Zr2O7 compact when sintered at 1500 °C, 4 h in air, achieved 99% theoretical density.

Effect of High Pressure on the Electrical Conductivity of TlInX2 (X = Se, Te) Layered Semiconductors

The dc electrical conductivity of TlInX2 (X = Se, Te) single crystals, parallel and perpendicular to the (001) c-axis is studied under high quasi-hydrostatic pressure up to 7.0 GPa, at room temperature. Conductivity measurements parallel to the c-axis are carried out at high pressures and down to liquid nitrogen temperatures. These materials show continuous metallization under pressure. Both compounds have almost the same pressure coefficient of the electrical activation energy parallel to the c-axis, d(ΔE∥)/dP = −2.9 × 10−10 eV/Pa, which results from the narrowing of the band gap under pressure. The results are discussed in the light of the band structure of these compounds.

Electronic structure of La1-xSrxFeO3

We have investigated the electronic structure of well-characterized samples of La1-xSrxFeO3 (x=0.0�0.4) by x-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy, bremsstrahlung isochromat (BI) spectroscopy, and Auger electron spectroscopy. We find systematic behavior in the occupied and unoccupied density of states reflecting changes in the electronic structure on hole doping via Sr substitution as well as providing estimates for different interaction strengths. The spectral features, particularly of the unoccupied states obtained from BI spectra, indicate the probable reason for the absence of an insulator-metal transition in this series. Analysis of the Auger spectra provides the estimates of the on-site effective Coulomb interaction strengths in Fe 3d and O 2p states. The parameter values for the bare charge-transfer energy ? and the Fe 3d�O 2p hybridization strength t? for LaFeO3 are obtained from an analysis of the Fe 2p core-level XPS in terms of a model many-body calculation. We discuss the character of the ground state in LaFeO3 as well as the nature of the doped hole states in La1-xSrxFeO3, based on these parameter values.

Electron spectroscopic investigation of the semiconductor-metal transition in La1-xSrxMnO3

We study the electronic structure of La1-xSrxMnO3+δ, x=0, 0.1, 0.2, 0.3, and 0.4, across the semiconductor-metal transition, using various electron spectroscopy techniques. The negligible intensity seen at EF using ultraviolet photoemission spectroscopy and bremsstrahlung isochromat spectroscopy (BIS) indicate an unusual semiconductor-metal transition observed for x≥0.2, consistent with the resistivity data. The BIS spectra show doped hole states developing about 1.4 eV above EF as a function of x. Auger electron spectroscopy gives an estimate of the intra-atomic Coulomb energy in the O 2p manifold to be about 6.8 eV. The Mn 2p core-level spectrum of LaMnO3, analyzed in terms of a configuration-interaction calculation, gives parameter values of the charge-transfer energy Δ=5.0 eV, the hybridization strength between Mn 3d and O 2p states, t=3.8 eV, and the on-site Coulomb energy in Mn 3d states Udd=4.0 eV, suggesting a mixed character for the ground state of LaMnO3.

Processing maps for hot-working of powder metallurgy 1100 Al-10 vol % SiC-particulate metal-matrix composite

The hot-working characteristics of the metal-matrix composite (MMC) Al-10 vol % SiC-particulate (SiCp) powder metallurgy compacts in as-sintered and in hot-extruded conditions were studied using hot compression testing. On the basis of the stress-strain data as a function of temperature and strain rate, processing maps depicting the variation in the efficiency of power dissipation, given by eegr = 2m/(m+1), where m is the strain rate sensitivity of flow stress, have been established and are interpreted on the basis of the dynamic materials model. The as-sintered MMC exhibited a domain of dynamic recrystallization (DRX) with a peak efficiency of about 30% at a temperature of about 500°C and a strain rate of 0.01 s�1. At temperatures below 350°C and in the strain rate range 0.001�0.01 s�1 the MMC exhibited dynamic recovery. The as-sintered MMC was extruded at 500°C using a ram speed of 3 mm s�1 and an extrusion ratio of 10ratio1. A processing map was established on the extruded product, and this map showed that the DRX domain had shifted to lower temperature (450°C) and higher strain rate (1 s�1). The optimum temperature and strain rate combination for powder metallurgy billet conditioning are 500°C and 0.01 s�1, and the secondary metal-working on the extruded product may be done at a higher strain rate of 1 s�1 and a lower temperature of 425°C.