Synthesis, crystal structure and catalytic properties of (p-cymene)ruthenium(II) azophenol complexes: azophenyl to azophenol conversion by oxygen insertion to a ruthenium---carbon bond

Azophenol complexes of formulation [(η6-p-cymene)RuCl(Ln)] (1–6, n=1–6) were prepared by two synthetic methods involving either an oxygen insertion to the Ru---C bond in cycloruthenated precursors forming complexes 1 and 2 or from the reaction of [{(η6-p-cymene)RuCl}2(μ-Cl)2] with azophenol ligands (HL3–HL6) in the presence of sodium carbonate in CH2Cl2. The molecular structure of the 1-(phenylazo)-2-naphthol complex has been determined by X-ray crystallography. The complex has a η6-p-cymene group, a chloride and a bidentate N,O-donor azophenol ligand. The complexes have been characterized from NMR spectral data. The catalytic activity of the complexes has been studied for the conversion of acetophenone to the corresponding alcohol in the presence of KOH and isopropanol. Complexes 4 and 6 having a methoxy group attached to the ortho-position of the phenylazo moiety and 2 with a methyl group in the meta-position of the phenolic moiety show high percentage conversion (>84%).

Formation of amorphous xenon nanoclusters and microstructure evolution in pulsed laser deposited Ti(62.5)Si(37.5) thin films during Xe ion irradiation

As deposited amorphous and crystallized thin films of Ti 37.5% Si alloy deposited by pulsed laser ablation technique were irradiated with 100 keV Xe(+) ion beam to an ion fluence of about 10(16) ions-cm(-2). Transmission electron microscopy revealed that the implanted Xe formed amorphous nanosized clusters in both cases. The Xe ion-irradiation favors nucleation of a fcc-Ti(Si) phase in amorphous films. However, in crystalline films, irradiation leads to dissolution of the Ti(5)Si(3) intermetallic phase. In both cases, Xe irradiation leads to the evolution of similar microstructures. Our results point to the pivotal role of nucleation in the evolution of the microstructure under the condition of ion implantation.

Characterization of vesicles from ion-paired gemini surfactants by small angle neutron scattering

Detailed small angle neutron scattering ( SANS) studies were carried out with the aqueous vesicular (unilamellar) suspension of dimeric ion-paired lipids (2a-2c) for spacer lengths corresponding to n-values of 2, 6 and 10 and monomeric ion-paired lipid (3) below and above the phase transition temperature of each amphiphile. The vesicular structure strongly depends on the spacer chain length. The mean vesicle size is smallest for the lipid with a short spacer, n = 3 and it increases with the increase in the spacer chain length. The bilayer thickness also decreases with the increase in the spacer chain length. The size polydispersity increases with the increase in the spacer chain length (n-value).

Properties of Al2O3 films prepared by argon ion assisted deposition

Aluminum oxide films have been prepared by ion assisted deposition using argon ions with energy in the range 300 to 1000 eV and current density in the range 50 to 220 μA/cm2. The influence of ion energy and current density on the optical and structural properties has been investigated. The refractive index, packing density, and extinction coefficient are found to be very sensitive to the ion beam parameters and substrate temperatures. The as-deposited films were found to be amorphous and could be transformed into crystalline phase on annealing. However, the crystalline phases were different in films prepared at ambient and elevated substrate temperatures.

Decomposition temperatures of Cu2Ln2O5 (Ln = Tb, Dy, Ho, Er, Tm, Yb, and Lu) compounds

The equilibrium decomposition temperatures of Cu2Ln2O5 (Ln = Tb, Dy, Ho, Er, Tm, Yb, and Lu) compounds have been measured using a combined DTA-TGA apparatus under a flowing Ar + O2 gas mixture, in which the partial pressure of oxygen was controlled at 5.0 × 103 Pa. The Cu2Ln2O5 compounds yield Ln2O3 and Cu2O on decomposition. The decomposition temperature increases monotonically with the atomic number of the lanthanide element. This suggests that the stability of the Cu2Ln2O5 compounds with respect to the component binary oxides increases with decreasing radius of the Ln3+ ion.

Kinetic decomposition of Ni2SiO4 in oxygen potential gradients

Nickel orthosilicate (Ni2SiO4) has been found to decompose into its component binary oxides in oxygen potential gradients at 1373 K. Nickel oxide was formed at the high oxygen potential boundary, while silica was detected at the low oxygen potential side. Significant porosity and fissures were observed near the Ni2SiO4/SiO2 interface and the SiO2 layer. The critical oxygen partial pressure ratio required for decomposition varied from 1.63 to 2.15 as the oxygen pressures were altered from 1.01 ⊠ 105 to 2.7X 10−4 Pa, well above the dissociation pressure of Ni2SiO4. Platinum markers placed at the boundaries of the Ni2SiO4 sample indicated growth of NiO at the higher oxygen potential boundary, without any apparent transport of material to the low oxygen potential side. However, significant movement of the bulk Ni2SiO4 crystal with respect to the marker was not observed. The decomposition of the silicate occurs due to the unequal rates of transport of Ni and Si. The critical oxygen partial pressure ratio required for decomposition is related both to the thermodynamic stability of Ni2SiO4 with respect to component oxides and the ratio of diffusivities of nickel and silicon. Kinetic decomposition of multicomponent oxides, first discovered by Schmalzried, Laqua, and co-workers [H. Schmalzried, W. Laqua, and P. L. Lin, Z. Natur Forsch. Teil A 34, 192 (1979); H. Schmalzried and W. Laqua, Oxid. Met. 15, 339 (1981); W. Laqua and H. Schmalzried, Chemical Metallurgy—A Tribute to Carl Wagner (Metallurgical Society of the AIME, New York, 1981), p. 29] has important consequences for their use at high temperatures and in geochemistry.

Epitaxial Growth of Co3O4 Films by Low Temperature, Low Pressure Chemical Vapor Deposition

The growth of strongly oriented or epitaxial thin films of metal oxides generally requires relatively high growth temperatures or infusion of energy to the growth surface through means such as ion bombardment. We have grown high quality epitaxial thin films of Co3O4 on different substrates at a temperature as low as 450°C by low-pressure metal-organic chemical vapor deposition (MOCVD) using cobalt(II) acetylacetonate as the precursor. With oxygen as the reactant gas, polycrystalline Co3O4 films are formed on glass and Si(100) in the temperature range 350-550°C. Under similar conditions of growth, highly oriented films of Co3O4 are formed on SrTiO3(100) and LaAlO3(100). The film on LaAlO3(100) grown at 450°C show a rocking curve FWHM of 1.61°, which reduces to 1.32° when it is annealed in oxygen at 725°C. The film on SrTiO3(100) has a FWHM of 0.330 (as deposited) and 0.29° (after annealing at 725°C). The ø-scan analysis shows cube-on-cube epitaxy on both these substrates. The quality of epitaxy on SrTiO3(100) is comparable to the best of the pervoskite-based oxide thin films grown at significantly higher temperatures.

Growth and study of BaZrO3 thin films by pulsed excimer laser ablation

Thin films of BaZrO3 (BZ) were grown using a pulsed laser deposition technique on platinum coated silicon substrates. Films showed a polycrystalline perovskite structure upon different annealing procedures of in-situ and ex-situ crystallization. The composition analyses were done using Energy dispersive X-ray analysis (EDAX) and Secondary ion mass spectrometry (SIMS). The SIMS analysis revealed that the ZrO2 formation at the right interface of substrate and the film leads the degradation of the device on the electrical properties in the case of ex-situ crystallized films. But the in-situ films exhibited no interfacial formation. The dielectric properties have been studied for the different temperatures in the frequency regime of 40 Hz to 100kHz. The response of the film to external ac stimuli was studied at different temperatures, and it showed that ac conductivity values in the limiting case are correspond to oxygen vacancy motion. The electrical modulus is fitted to a stretched exponential function and the results clearly indicate the presence of the non-Debye type of dielectric relaxation in these materials.

Formation of amorphous xenon nanoclusters and microstructure evolution in pulsed laser deposited Ti62.5Si37.5 thin films during Xe ion irradiation

As deposited amorphous and crystallized thin films of Ti 37.5% Si alloy deposited by pulsed laser ablation technique were irradiated with 100 keV Xe+ ion beam to an ion fluence of about 1016 ions-cm−2. Transmission electron microscopy revealed that the implanted Xe formed amorphous nanosized clusters in both cases. The Xe ion-irradiation favors nucleation of a fcc-Ti(Si) phase in amorphous films. However, in crystalline films, irradiation leads to dissolution of the Ti5Si3 intermetallic phase. In both cases, Xe irradiation leads to the evolution of similar microstructures. Our results point to the pivotal role of nucleation in the evolution of the microstructure under the condition of ion implantation.

A Study of Nanostructures of Thin Films in B–C–N System Produced by Pulsed Laser Deposition and Nitrogen Ion-Beam-Assisted Pulsed Laser Deposition

We report the synthesis of thin films of B–C–N and C–N deposited by N+ ion-beam-assisted pulsed laser deposition (IBPLD) technique on glass substrates at different temperatures. We compare these films with the thin films of boron carbide synthesized by pulsed laser deposition without the assistance of ion-beam. Electron diffraction experiments in the transmission electron microscope shows that the vapor quenched regions of all films deposited at room temperature are amorphous. In addition, shown for the first time is the evidence of laser melting and subsequent rapid solidification of B4C melt in the form of micrometer- and submicrometer-size round particulates on the respective films. It is possible to amorphize B4C melt droplets of submicrometer sizes. Solidification morphologies of micrometer-size droplets show dispersion of nanocrystallites of B4C in amorphous matrix within the droplets. We were unable to synthesize cubic carbon nitride using the current technique. However, the formation of nanocrystalline turbostratic carbo- and boron carbo-nitrides were possible by IBPLD on substrate at elevated temperature and not at room temperature. Turbostraticity relaxes the lattice spacings locally in the nanometric hexagonal graphite in C–N film deposited at 600 °C leading to large broadening of diffraction rings.

High energy Li ion irradiation effects in ferroelectric PZT and SBT thin films

The ferroelectric Pb(Zr0.53Ti0.47)O-3 (PZT) and SrBi2Ta2O9 (SBT) thin films were prepared by laser ablation technique. The dielectric analysis, capacitance-voltage, ferroelectric hysteresis and DC leakage current measurements were performed before and after 50 MeV Li3+ ion irradiation. In both thin films, the irradiation produced some amount of amorphisation, considerable degradation in the ferroelectric properties and change in DC conductivity. On irradiation of these thin films, the phase transition temperature [T-c] of PZT decreased considerably from 628 to 508 K, while SBT exhibited a broad and diffuse transition with its T-c decreased from 573 to 548 K. The capacitance-voltage curve at 100 kHz showed a double butterfly loop with a large decrease in the capacitance and switching voltage. There was decrease in the ferroelectric hysteresis loop, remanant polarisation and coercive field. After annealing at a temperature of 673 K for 10 min while PZT partially regained the ferroelectric properties, while SBT did not. The DC conductivity measurements showed a shift in the onset of non-linear conduction region in irradiated SBT. The degradation of ferroelectric properties of the irradiated thin films is attributed to the irradiation-induced partial amorphization and the pinning of the ferroelectric domains by trapped charges. The regaining of properties after annealing is attributed to the thermal annealing of the defects generated during the irradiation. (C) 2003 Elsevier Science B.V. All rights reserved.

Pt-Au/C cathode with enhanced oxygen-reduction activity in PEFCs

Carbon-supported Pt-Au (Pt-Au/C) catalyst is prepared separately by impregnation, colloidal and micro-emulsion methods, and characterized by physical and electrochemical methods. Highest catalytic activity towards oxygen-reduction reaction (ORR) is exhibited by Pt-Au/C catalyst prepared by colloidal method. The optimum atomic ratio of Pt to Au in Pt-Au/C catalyst prepared by colloidal method is determined using linear-sweep and cyclic voltammetry in conjunction with cell-polarization studies. Among 3:1, 2:1 and 1:1 Pt-Au/C catalysts, (3:1) Pt-Au/C exhibits maximum electrochemical activity towards ORR. Powder X-ray diffraction pattern and transmission electron micrograph suggest Pt-Au alloy nanoparticles to be well dispersed onto the carbon-support. Energy dispersive X-ray analysis and inductively coupled plasma-optical emission spectroscopy data suggest that the atomic ratios of the alloying elements match well with the expected values. A polymer electrolyte fuel cell (PEFC) operating at 0 center dot 6 V with (3:1) Pt-Au/C cathode delivers a maximum power-density of 0 center dot 65 W/cm (2) in relation to 0 center dot 53 W/cm (2) delivered by the PEFC with pristine carbon-supported Pt cathode.