EPR study of trap-centres produced on TiO2 particles during water photolysis

The results of an EPR investigation are presented on the paramagnetic trap-centres produced on hydrothermally prepared TiO2 particles during water photolysis at room temperature under band-gap irradiation. The trapped holes correspond to O− species adjacent to cation vacancies that are formed to compensate the hydroxyl ions in the subsurface layers. The trapped electrons are accounted for as Ti3+ in the conduction band or Ti3+ - adjoining oxygen vacancy to form shallow donor states. Although hole-centres are normally stabler than electron-centres, strongly adsorbed donor molecules reverse the stability. Concentration of hole-centres is increased by the presence of platinum on TiO2 surface and electron-centres are not detected on Pt/TiO2 during water photolysis.

Hydrothermal preparation of Ba(Ti,Zr)O3 fine powders

Fine powders consisting of aggregated submicron crystallites of Ba(Ti,Zr)O3 in the complete range of Ti/Zr ratios are prepared at 85–130°C by hydrothermal method, starting from TiO2 + ZrO2 · xH2O mixed gel and Ba(OH)2 solution. The products obtained below 110°C incorporate considerable amounts of H2O and OH− within the lattice. As-prepared BaTiO3 is cubic and converts to tetragonal phase after the heat treatment at 1200°C, accompanied by the loss of residual hydroxyl ions. TEM investgations of the growth features show a transformation of the gel to the crystallite. Ba2+ ions entering the gel produce chemical changes within the gel, followed by dehydration, resulting in a cubic perovskite phase irrespective of Ti/Zr. The sintering properties of these powders to fine-grained, high density ceramics and their dielectric properties are presented.

Characterization of barium titanate fine powders formed from hydrothermal crystallization

A detailed evaluation of size, shape and microstrains of BaTiO3 crystallites produced by hydrothermal crystallization at 90 – 180 °C and 0.1 – 1.2 MPa, from amorphous TiO2· xH2O (3 < × < 8) gel and aqueous Ba(OH)2 is presented, using X-ray line-broadening and TEM studies. Whereas the concentration of Ba(OH)2 and the acceptor impurities affect the crystallite shape, the stoichimetry with respect to Ba/Ti, donor as well as acceptor impurities, and the temperature of crystallization influence the microstrains. It is shown that strains in the crystallites are related to the point defects in the lattice. Compensation of the residually present hydroxyl ions in the oxygen sublattice by cation vacancies results in strains leading to metastable presence of the cubic phase at room temperature. Studies on the diffuse phase transition behaviour of these submicron powders show that the stable tetragonal phase is produced only on annealing at high temperatures where the mobility of cations vacancies are larger. Heat-treatment reduces anisotropy and strain in undoped samples, whereas annealing is less effective in doped materials. Comparison of the crystillite size by TEM showed better agreement with the Warren—Averbach method.

In-situ crystallization studies of gels in the ZrO2---SiO2 system

The in-situ investigation of amorphous gels is important in understanding the evolution of structures and the influence of environmental factors on crystallization. In this paper, the ZrO2---SiO2 system has been studied in-situ under electron beam heating. The study reveals that both the size of the ZrO2 particles and the presence of hydroxyl ions influence the nature of the crystalline phase of the ZrO2 particles formed.

On the existence of hydrotalcite-like phases in the absence of trivalent cations

alpha-Hydroxides of nickel(II) and cobalt(II) are hydrotalcite-like phases, possessing a layered double hydroxide (LDH) structure even though there are no trivalent cations in the lattice. While the LDHs acquire a positive charge on the hydroxide layers by the incorporation of trivalent cations, we suggest that the alpha-hydroxides acquire a positive charge by partial protonation of the hydroxyl ions according to the equation M(OH)(2)+xH(+) --> [M(OH)(2-x)(H2O)(x)](x+). As in the LDHs, charge balance is restored by the incorporation of anions in the interlayer region. (C) 1997 Academic Press.

Spectroscopic investigations of manganese ions in microwave-prepared NaPO3-PbO glasses

The EPR spectra of microwave-prepared 70NaPO(3):30PbO glasses containing different weight percentages of manganese ions have been studied. The EPR spectra exhibit a well-resolved hyperfine pattern at g(eff) approximate to 2.0. Optical absorption, fluorescent emission and excitation spectra of the glasses have been examined. The absorption spectrum exhibits a peak near 500 nm and this has been attributed to the spin-allowed E-5(g) --> T-5(2g) transition of Mn3+ ions. The emission spectrum shows a band at 595 nm which has been assigned to the T-4(1g)(G) --> (6)A(1g)(S) spin-forbidden transition of Mn2+ ions in octahedral coordination. Concentration quenching of fluorescence was found to occur above 0.75 wt% of Mn2+ ions. The excitation spectra exhibit four bands characteristic of Mn2+ ions in octahedral coordination. From the observed band positions of the excitation spectra, the crystal field parameter D-q and the Racah interelectronic repulsion parameters, B and C have been calculated. A structural model is proposed based on the IR, Raman and MASNMR studies according to which Mn2+ ions are likely to occupy sites similar to Na+ ions in these glasses.

Synthesis of some copper(II)-chelating (dialkylamino)pyridine amphiphiles and evaluation of their esterolytic capacities in cationic micellar media

Three new (dialkylamino)pyridine (DAAP)-based ligand amphiphiles 3-5 have been synthesized. All of the compounds possess a metal ion binding subunit in the form of a 2,6-disubstituted DAAP moiety. In addition, at least one ortho-CH2OH substituent is present in all the ligands. Complex formation by these ligands with various metal ions were examined under micellar conditions, but only complexes with Cu(II) ions showed kinetically potent esterolytic capacities under micellar conditions. Complexes with Cu(II) were prepared in host comicellar cetyltrimethylammonium bromide (CTABr) media at pH 7.6. Individual complexes were characterized by UV-visible absorption spectroscopy and electron paramagnetic resonance spectroscopy. These metallomicelles speed the cleavage of the substrates p-nitrophenyl hexanoate or p-nitrophenyl diphenyl phosphate. To ascertain the nature of the active esterolytic species, the stoichiometries of the respective Cu(II) complexes were determined from the kinetic version of Job's plot. In all the instances, 2:1 complex ligand/Cu(II) ion are the most kinetically competent species. The apparent pK(a) values of the Cu(II)-coordinated hydroxyl groups of the ligands 3, 4, and 5, in the comicellar aggregate, are 7.8, 8.0, and 8.0, respectively, as estimated from the rate constant vs pH: profiles of the ester cleavage reactions. The nucleophilic metallomicellar reagents and the second-order "catalytic" rate constants toward esterolysis of the substrate p-nitrophenyl hexanoate (at 25 degrees C, pH 7.6) are 37.5 for 3, 11.4 for 4, and 13.8 for 5. All catalytic systems comprising the coaggregates of 3, 4, or 5 and CTABr demonstrate turnover behavior in the presence of excess substrate.

Soft-particle model analysis of effect of LPS on electrophoretic softness of Acidithiobacillus ferrooxidans grown in presence of different metal ions

The effect of Surface lipopolysaccharides (LPS) on the electrophoretic softness and fixed charge density in the ion-penetrable layer of Acidithiobacillus ferrooxidans cells grown in presence of copper or arsenic ions have been discussed, The electrophoretic mobility data were analyzed using the soft-particle electrophoresis theory. Cell surface potentials of all the strains based on soft-particle theory were lower than those estimated using the conventional Smoluchowski theory, Exposure to metal ions increased the Surface electrophoretic softness with decrease in the fixed charge density. Effect of cell surface lipopolysaccharides on the model parameters are investigated and discussed.

Co-2-Ions In A Low-Pressure Glow-Discharge Of Carbon-Dioxide

$CO_2^{-}$ ions have been detected in the gas phase and measured by a mass spectrometer with a flight time of 30 µs in the positive column of carbondioxide glow discharge.

EPR observation of phase transitions in calcium cadmium acetate hexahydrate: Using Mn2+ and Cu2+ ions as probe

Results of temperature dependence of EPR spectra of Mn2+ and Cu2+ ions doped calcium cadmium acetate hexahydrate (CaCd(CH3COO)4•6H2O) have been reported. The investigation has been carried out in the temperature range between room temperature ( 300 K) and liquid nitrogen temperature. A I-order phase transition at 146 ± 0.5 K has been confirmed. In addition a new II-order phase transition at 128 ± 1 K has been detected for the first time. There is evidence of large amplitude hindered rotations of CH3 groups which become frozen at 128 K. The incorporation of Cu2+ and Mn2+ probes at Ca2+ and Cd2+ sites respectively provide evidence that the phase transitions are caused by the molecular rearrangements of the common coordinating acetate groups between Ca2+ and Cd2+ sites. In contradiction to the previous reports of a change of symmetry from tetragonal to orthorhombic below 140 K, the symmetry of the host is concluded to remain tetragonal in all the three observed phases between room temperature and liquid nitrogen temperature.

Ions And Barriers in Electric Discharge

It is a well know that electrons and positive ions are responsible in the case of electric spark. Investigation have been undertaken in the high voltage laboratory to study the effect of injecting ions (both possitive and negative)into the spark gap.Also the effect of paper screens in blocking the ions being invetsigated.

05-ions in a low pressure glow discharge of oxygen

0:- ions have been detected and measured in a positive column of glow discharge in oxygen between 0.04 and 0.17 Torr. A suitable ion-molecule reaction has been proposed, which appears to be supported by the mass spectrometer measurements.

Ammonium ions prevent methylation of uridine to ribothymidine in Azotobacter vinelandii tRNA

It was shown that tRNA from Azotobacter vinelandii grown in the presence of ammonium chloride lacks ribothymidine while that grown in the absence of the ammonium salt contains this modified nucleoside. [32P]-Labelled tRNA from this organism grown in a medium containing the ammonium salt was digested with RNase T1 and the pseudouridinecontaining tetranucleotide, common to all tRNAs was isolated and analysed for the nucleoside replacing the ribothymidine. It was found to be uridine. Cells previously labelled with [32P]- phosphate in the ammonium salt medium were washed and incubated in the ammonium saltfree medium to test whether ribothymidine would be formed upon removal of the ammoniumions. Methylation of the uridine did not take place.

Facile conversion of electron rich benzylic hydrocarbons to carbonyl compounds by peroxydisulphate and copper ions

A convenient method for the conversion of electron rich benzylic hydrocarbons to carbonyl compounds is reported.